Fungicidal amides

ABSTRACT

Disclosed are compounds of Formula 1, including all stereoisomers, N-oxides, and salts thereof, 
     
       
         
         
             
             
         
       
     
     wherein
         G is phenyl, pyridinyl, pyridazinyl or pyrazinyl substituted with Q meta or para to the —C(R 2a )R 2b — radical, and optionally substituted with up to 3 substituents selected from R 3 ;   and A, Z, R 1 , R 2a , R 2b , R 3  and Q are as defined in the disclosure.       

     Also disclosed are compositions containing the compounds of Formula 1 and methods for controlling plant disease caused by a fungal plant pathogen comprising applying an effective amount of a compound or a composition of the invention.

FIELD OF THE INVENTION

This invention relates to certain fungicidal amides, their N-oxides,salts and compositions, and methods of their use as fungicides.

BACKGROUND OF THE INVENTION

The control of plant diseases caused by fungal plant pathogens isextremely important in achieving high crop efficiency. Plant diseasedamage to ornamental, vegetable, field, cereal, and fruit crops cancause significant reduction in productivity and thereby result inincreased costs to the consumer. Many products are commerciallyavailable for these purposes, but the need continues for new compoundswhich are more effective, less costly, less toxic, environmentally saferor have different sites of action.

SUMMARY OF THE INVENTION

This invention is directed to compounds of Formula 1 (including allstereoisomers), N-oxides, and salts thereof, agricultural compositionscontaining them and their use as fungicides:

wherein

-   -   A is a radical selected from the group consisting of

-   -   Z is O or S;    -   R¹ is C₃-C₅ cycloalkyl; or a 4- to 6-membered ring containing        ring members selected from carbon atoms, 1O atom and 1S atom;    -   R^(2a) and R^(2b) are each independently H, halogen, C₁-C₂ alkyl        or C₁-C₂ haloalkyl; or    -   R^(2a) and R^(2b) are taken together as C₂-C₅ alkanediyl;    -   G is phenyl, pyridinyl, pyridazinyl or pyrazinyl substituted        with Q meta or para to the —C(R^(2a))R^(2b)— radical, and        optionally substituted with up to 3 substituents selected from        R³;    -   R³ is halogen, nitro, cyano, C₁-C₅ cyanoalkoxy, C₂-C₅        alkynyloxy, C₂-C₅ alkenyl, C₁-C₅ alkyl, C₁-C₅ haloalkyl, C₁-C₅        alkoxy, C₁-C₅ haloalkoxy, C₂-C₅ alkoxyalkyl, C₃-C₅ cycloalkyl,        C₂-C₅ alkoxycarbonyl or C₃-C₁₂ trialkylsilyl;    -   R⁴ is halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl;    -   R⁵ is H, halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl;    -   R⁶ is C₁-C₂ alkyl;    -   R⁷ is halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl;    -   R⁸ is H, C₁-C₂ alkyl or C₁-C₂ haloalkyl;    -   R⁹ is halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl;    -   R¹⁰ is halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl;    -   R¹¹ is halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl;    -   m is 0, 1 or 2;    -   Q is a 5-membered unsaturated or partially unsaturated        heterocyclic ring containing ring members selected from carbon        atoms and up to 4 heteroatoms independently selected from up to        1O, up to 1S and up to 4 N atoms, wherein up to 2 carbon atom        ring members are independently selected from C(═O), the ring        optionally substituted with one substituent on a ring member        distal relative to the ring member connecting the heteroaromatic        ring to the remainder of Formula 1, said optional substituent        selected from R^(12c) on carbon atom ring members and from        R^(12n) on nitrogen atom ring members, the heterocyclic ring        further optionally substituted with substituents selected from        R^(13c) on carbon atom ring members and R^(13n) on nitrogen atom        ring members;    -   each R^(12c) is independently halogen, cyano, C₁-C₃ alkyl, C₁-C₃        haloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy or C₂-C₃        alkoxycarbonyl; or a phenyl ring optionally substituted with up        to 5 substituents independently selected from R¹⁴; or a        heteroaromatic ring optionally substituted with up to 4        substituents independently selected from R^(15c) on carbon atom        ring members and from R^(15n) on nitrogen atom ring members; or    -   two R^(12c) bonded to adjacent carbon atoms are taken together        with carbon atom ring members to form a 5- or 6-membered        carbocyclic or partially aromatic ring;    -   each R^(12n) is independently C₁-C₃ alkyl, C₁-C₃ haloalkyl or        C₁-C₃ alkoxy; or a phenyl ring optionally substituted with up to        5 substituents independently selected from R¹⁶; or a        heteroaromatic ring optionally substituted with up to 4        substituents independently selected from R^(17c) on carbon atom        ring members and from R^(17n) on nitrogen atom ring members;    -   each R^(13c) is independently halogen, C₁-C₃ alkyl, C₁-C₃        haloalkyl or C₁-C₃ alkoxy;    -   each R^(13n) is independently C₁-C₃ alkyl, C₁-C₃ haloalkyl or        C₁-C₃ alkoxy;    -   each R¹⁴, R^(15c), R¹⁶ and R^(17c) is independently halogen,        cyano, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy or C₁-C₂        haloalkoxy; and    -   each R^(15n) and R^(17n) is independently C₁-C₂ alkyl, C₁-C₂        haloalkyl or C₁-C₂ alkoxy.

More particularly, this invention pertains to a compound of Formula 1(including all stereoisomers), an N-oxide or a salt thereof.

This invention also relates to a fungicidal composition comprising (a) acompound of the invention (i.e. in a fungicidally effective amount); and(b) at least one additional component selected from the group consistingof surfactants, solid diluents and liquid diluents.

This invention also relates to a fungicidal composition comprising (a) acompound of the invention; and (b) at least one other fungicide (e.g.,at least one other fungicide having a different site of action).

This invention further relates to a method for controlling plantdiseases caused by fungal plant pathogens comprising applying to theplant or portion thereof, or to the plant seed, a fungicidally effectiveamount of a compound of the invention (e.g., as a composition describedherein).

DETAILS OF THE INVENTION

As used herein, the terms “comprises,” “comprising,” “includes,”“including,” “has,” “having,” “contains”, “containing,” “characterizedby” or any other variation thereof, are intended to cover anon-exclusive inclusion, subject to any limitation explicitly indicated.For example, a composition, mixture, process, method, article, orapparatus that comprises a list of elements is not necessarily limitedto only those elements but may include other elements not expresslylisted or inherent to such composition, mixture, process, method,article, or apparatus.

The transitional phrase “consisting of” excludes any element, step, oringredient not specified. If in the claim, such would close the claim tothe inclusion of materials other than those recited except forimpurities ordinarily associated therewith. When the phrase “consistingof” appears in a clause of the body of a claim, rather than immediatelyfollowing the preamble, it limits only the element set forth in thatclause; other elements are not excluded from the claim as a whole.

The transitional phrase “consisting essentially of” is used to define acomposition, method or apparatus that includes materials, steps,features, components, or elements, in addition to those literallydisclosed, provided that these additional materials, steps, features,components, or elements do not materially affect the basic and novelcharacteristic(s) of the claimed invention. The term “consistingessentially of” occupies a middle ground between “comprising” and“consisting of”.

Where applicants have defined an invention or a portion thereof with anopen-ended term such as “comprising,” it should be readily understoodthat (unless otherwise stated) the description should be interpreted toalso describe such an invention using the terms “consisting essentiallyof” or “consisting of.”

Further, unless expressly stated to the contrary, “or” refers to aninclusive or and not to an exclusive or. For example, a condition A or Bis satisfied by any one of the following: A is true (or present) and Bis false (or not present), A is false (or not present) and B is true (orpresent), and both A and B are true (or present).

Also, the indefinite articles “a” and “an” preceding an element orcomponent of the invention are intended to be nonrestrictive regardingthe number of instances (i.e. occurrences) of the element or component.Therefore “a” or “an” should be read to include one or at least one, andthe singular word form of the element or component also includes theplural unless the number is obviously meant to be singular.

As referred to in the present disclosure and claims, “plant” includesmembers of Kingdom Plantae, particularly seed plants (Spermatopsida), atall life stages, including young plants (e.g., germinating seedsdeveloping into seedlings) and mature, reproductive stages (e.g., plantsproducing flowers and seeds). Portions of plants include geotropicmembers typically growing beneath the surface of the growing medium(e.g., soil), such as roots, tubers, bulbs and corms, and also membersgrowing above the growing medium, such as foliage (including stems andleaves), flowers, fruits and seeds. As referred to herein, the term“seedling”, used either alone or in a combination of words means a youngplant developing from the embryo of a seed. In the context of thisdisclosure, plant disease control refers to protecting plantspreventatively and/or curatively from diseases caused by pathogens. Asreferred to in this disclosure, the terms “fungal pathogen” and “fungalplant pathogen” include pathogens in the Ascomycota, Basidiomycota andZygomycota phyla, and the fungal-like Oomycota class that are the causalagents of a broad spectrum of plant diseases of economic importance,affecting ornamental, turf, vegetable, field, cereal and fruit crops. Inthe context of this disclosure, “protecting a plant from disease” or“control of a plant disease” includes preventative action (interruptionof the fungal cycle of infection, colonization, symptom development andspore production) and/or curative action (inhibition of colonization ofplant host tissues).

As referred to in this disclosure, the term mode of action (MOA) is asdefined broadly by the Fungicide Resistance Action Committee (FRAC), andis used to distinguish fungicide groups according to their biochemicalmode of action in the biosynthetic pathways of plant pathogens. TheseFRAC-defined MOAs are (A) nucleic acid synthesis, (B) mitosis and celldivision, (C) respiration, (D) amino acid and protein synthesis, (E)signal transduction, (F) lipid synthesis and membrane integrity, (G)sterol biosynthesis in membranes, (H) cell wall biosynthesis inmembranes, (I) melanin synthesis in cell wall, (P) host plant defenseinduction, multi-site contact activity and unknown mode of action. EachMOA class consists of one or more groups based either on individualvalidated target sites of action, or in cases where the precise targetsite is unknown, based on cross resistance profiles within a group or inrelation to other groups. Each of these groupings within a FRAC-definedMOA, whether the target site is known or unknown, is designated by aFRAC code. Additional information on target sites and FRAC codes can beobtained from publicly available databases maintained, for example, byFRAC.

As referred to in this disclosure, the term “cross resistance” refers toa phenomenon wherein a pathogen evolves resistance to one fungicide andin addition acquires resistance to others. These additional fungicidesare typically, but not always, in the same chemical class or have thesame target site of action, or can be detoxified by the same mechanism.

In the above recitations, the term “alkyl”, used either alone or incompound words such as “alkylthio” or “haloalkyl” includesstraight-chain or branched alkyl such as methyl, ethyl, n-propyl,i-propyl, or the different butyl, pentyl or hexyl isomers. “Alkenyl”includes straight-chain or branched alkenes such as ethenyl, 1-propenyl,2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.“Alkenyl” also includes polyenes such as 1,2-propadienyl and2,4-hexadienyl. “Alkynyl” includes straight-chain or branched alkynessuch as ethynyl, 1-propynyl, 2-propynyl and the different butynyl,pentynyl and hexynyl isomers. “Alkynyl” also includes moieties comprisedof multiple triple bonds such as 2,5-hexadiynyl. “Alkanediyl” denotes astraight-chain or branched alkylene. Examples of “alkanediyl” includeCH₂, CH₂CH₂, CH(CH₃), CH₂CH₂CH₂, CH₂CH(CH₃), and the different butyleneisomers. “Trialkylsilyl” includes 3 branched and/or straight-chain alkylradicals attached to and linked through a silicon atom, such astrimethylsilyl, triethylsilyl and tert-butyldimethylsilyl. “Alkoxy”includes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy andthe different butoxy, pentoxy and hexyloxy isomers. “Alkoxyalkyl”denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” includeCH₃OCH₂, CH₃OCH₂CH₂, CH₃CH₂OCH₂, CH₃CH₂CH₂CH₂OCH₂ and CH₃CH₂OCH₂CH₂.“Alkoxyalkoxy” denotes alkoxy substitution on alkoxy. “Alkenyloxy”includes straight-chain or branched alkenyloxy moieties. Examples of“alkenyloxy” include H₂C═CHCH₂O, (CH₃)₂C═CHCH₂O, (CH₃)CH═CHCH₂O,(CH₃)CH═C(CH₃)CH₂O and CH₂═CHCH₂CH₂O. “Alkynyloxy” includesstraight-chain or branched alkynyloxy moieties. Examples of “alkynyloxy”include HCCCH₂O, CH₃CCCH₂O and CH₃CCCH₂CH₂O. “Alkylthio” includesbranched or straight-chain alkylthio moieties such as methylthio,ethylthio, and the different propylthio, butylthio, pentylthio andhexylthio isomers. “Alkylsulfinyl” includes both enantiomers of analkylsulfinyl group. Examples of “alkylsulfinyl” include CH₃S(O)—,CH₃CH₂S(O)—, CH₃CH₂CH₂S(O)—, (CH₃)₂CHS(O)— and the differentbutylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of“alkylsulfonyl” include CH₃S(O)₂—, CH₃CH₂S(O)₂—, CH₃CH₂CH₂S(O)₂—,(CH₃)₂CHS(O)₂—, and the different butylsulfonyl, pentylsulfonyl andhexylsulfonyl isomers. “Alkylthioalkyl” denotes alkylthio substitutionon alkyl. Examples of “alkylthioalkyl” include CH₃SCH₂, CH₃SCH₂CH₂,CH₃CH₂SCH₂, CH₃CH₂CH₂CH₂SCH₂ and CH₃CH₂SCH₂CH₂. “Alkylthioalkoxy”denotes alkylthio substitution on alkoxy. “Alkyldithio” denotes branchedor straight-chain alkyldithio moieties. Examples of “alkyldithio”include CH₃SS—, CH₃CH₂SS—, CH₃CH₂CH₂SS—, (CH₃)₂CHSS— and the differentbutyldithio and pentyldithio isomers. “Cyanoalkyl” denotes an alkylgroup substituted with one cyano group. Examples of “cyanoalkyl” includeNCCH₂, NCCH₂CH₂ and CH₃CH(CN)CH₂. “Cyanoalkoxy”, “dialkylamino”,“alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”, “alkynylthio”,“alkynylsulfinyl”, “alkynylsulfonyl”, and the like, are definedanalogously to the above examples. Examples of “cyanoalkoxy” includeCNCH₂O and CNCH₂CH₂O.

“Cycloalkyl” includes, for example, cyclopropyl, cyclobutyl, cyclopentyland cyclohexyl. The term “alkylcycloalkyl” denotes alkyl substitution ona cycloalkyl moiety and includes, for example, ethylcyclopropyl,i-propylcyclobutyl, 3-methylcyclopentyl and 4-methylcyclohexyl. The term“cycloalkylalkyl” denotes cycloalkyl substitution on an alkyl moiety.Examples of “cycloalkylalkyl” include cyclopropylmethyl,cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chainor branched alkyl groups. The term “cycloalkoxy” denotes cycloalkyllinked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.“Cycloalkylalkoxy” denotes cycloalkylalkyl linked through an oxygen atomattached to the alkyl chain. Examples of “cycloalkylalkoxy” includecyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moietiesbonded to straight-chain or branched alkoxy groups.

The term “halogen”, either alone or in compound words such as“haloalkyl”, includes fluorine, chlorine, bromine or iodine.“Haloalkoxy”, is defined analogously to the term “haloalkyl”.

The total number of carbon atoms in a substituent group is indicated bythe “C_(i)-C_(j)” prefix where i and j are numbers from 1 to 5. Forexample, C₁-C₃ alkoxy designates CH₃O—, CH₃CH₂O—, CH₃CH₂CH₂O— and(CH₃)₂CHO—.

“Aromatic” indicates that each of the ring atoms is essentially in thesame plane and has a p-orbital perpendicular to the ring plane, and that(4 n+2) π electrons, where n is a positive integer, are associated withthe ring to comply with Hückel's rule. When a fully unsaturatedcarbocyclic ring satisfies Hückel's rule, then said ring is also calledan “aromatic ring. When a fully unsaturated heterocyclic ring satisfiesHückel's rule, then said ring is also called a “heteroaromatic ring” Theterm “nonaromatic heterocyclic ring” denotes a heterocyclic ring systemin which no ring in the ring system is aromatic.

The term “optionally substituted” in connection with the heterocyclicrings refers to groups which are unsubstituted or have at least onenon-hydrogen substituent that does not extinguish the biologicalactivity possessed by the unsubstituted analog. As used herein, thefollowing definitions shall apply unless otherwise indicated. The term“optionally substituted” is used interchangeably with the phrase“substituted or unsubstituted” or with the term “(un)substituted.”Unless otherwise indicated, an optionally substituted group may have asubstituent at each substitutable position of the group, and eachsubstitution is independent of the other.

When a compound is substituted with a substituent bearing a subscriptthat indicates the number of said substituents can exceed 1, saidsubstituents (when they exceed 1) are independently selected from thegroup of defined substituents, e.g., (R³)_(n), n is 0, 1, 2 or 3. When agroup contains a substituent which can be hydrogen, for example R^(2a),then when this substituent is taken as hydrogen, it is recognized thatthis is equivalent to said group being unsubstituted. When a variablegroup is shown to be optionally attached to a position, for example(R³)_(n), wherein n may be 0, then hydrogen may be at the position evenif not recited in the variable group definition. When one or morepositions on a group are said to be “not substituted” or“unsubstituted”, then hydrogen atoms are attached to take up any freevalency.

As referred to by the present disclosure and claims, an “unsaturatedheterocyclic ring” is a heterocyclic ring wherein at least two ringmember atoms are linked together by a double bond. Unless otherwisestated, an “unsaturated or partially unsaturated heterocyclic ring”(e.g., substituent Q) may be partially unsaturated or fully unsaturated.The expression “fully unsaturated heterocyclic ring” means aheterocyclic ring of atoms in which the bonds between carbon and/ornitrogen atoms in the ring are single or double bonds according tovalence bond theory and furthermore the bonds between carbon and/ornitrogen atoms in the ring include as many double bonds as possiblewithout double bonds being cumulative (i.e. no C═C═C, N═C═C, etc.). Theterm “partially unsaturated heterocyclic ring” denotes a heterocyclicring comprising at least one ring member bonded to an adjacent ringmember through a double bond and which conceptually potentiallyaccommodates a number of non-cumulated double bonds between adjacentring members (i.e. in its fully unsaturated counterpart form) greaterthan the number of double bonds present (i.e. in its partiallyunsaturated form). In the Summary of the Invention R¹ can be inter aliaa 4- to 6-membered ring containing ring members selected from carbonatoms, 1O atom and 1S atom. This ring is understood to be a carbocyclicring and includes a non-carbon ring member selected from 1O atom or 1Satom. Examples of a 4-membered ring containing ring members selectedfrom carbon atoms, 1O atom and 1S atom include an oxetane ring (i.e.2-oxetanyl or 3-oxetanyl) or a thietane ring (i.e. 2-thietanyl or3-thietanyl). Examples of a 5-membered ring containing ring membersselected from carbon atoms, 1O atom and 1S atom include the variousregioisomers or tetrahydrofuran or tetrahydrothiophene. Examples of a6-membered ring containing ring members selected from carbon atoms, 1Oatom and 1S atom include the various regioisomers of pyran andthiopyran. Note that the attachment point of these rings to theremainder of a Formula 1 can be through any available carbon atom withfree valency.

In the Summary of the Invention the unsaturated heterocyclic ring of Qis specified to be 5-membered, with ring members selected from carbonatoms and up to 4 heteroatoms independently selected from up to 1O, upto 1S and up to 4 N atoms, wherein up to 2 carbon atoms areindependently selected from C(═O). The heterocyclic ring is optionallysubstituted with one substituent on a ring member distal relative to thering member connecting the heteroaromatic ring to the remainder ofFormula 1. As depicted in Exhibit 1, the five-membered heterocyclic ringof Q, a ring member distal relative to the ring member connecting thering to the remainder of Formula 1 is linked through two ring bonds toconnecting ring member. The heterocyclic ring of Q is further optionallysubstituted with substituents selected from R^(12c) on carbon atom ringmembers and R^(12n) on nitrogen atom ring members.

Certain heterocycles forming Q may have two distal ring membersavailable for substitution. In this situation, only one of the distalring members may be substituted with R^(12c) or R^(12n); the otherdistal ring member may be substituted with R^(13c) or R^(13n). Ifneither of the distal ring members of a heterocycle forming Q areavailable for substitution, then any additional substituents on theheterocycle are selected from R^(13c) or R^(13n). If a distal ringmember can have two substituents, one substituent may be selected fromR^(12c) or R^(12n) and the other substituent may be selected fromR^(13c) or R^(13n). In other words, the Q ring is limited to one R^(12c)or R^(12n) substituent and this substituent must be bonded to a distalring member; the Q ring can otherwise be further substituted withR^(13c) or R^(13n) on any available ring member.

If an attachment point on a group (e.g., ring) is depicted as floating(e.g., as illustrated by the 5-membered unsaturated or partiallysaturated heterocyclic rings Q-1 through Q-21 in Exhibit 3), the groupcan be attached to the remainder of Formula 1 through any availablecarbon or nitrogen of the group by replacement of a hydrogen atom. Ifthe attachment point of a substituent on a group (e.g., ring) isdepicted as floating (e.g., as illustrated for R¹² and R¹³ on the5-membered unsaturated heterocyclic rings Q-1 through Q-21 in Exhibit 3of Embodiment 54), the substituent can be attached to any availablecarbon or nitrogen atom by replacing a hydrogen atom.

In the Summary of the Invention G can be phenyl, pyridinyl, pyridazinylor pyrazinyl substituted with Q meta or para to the —C(R^(2a))R^(2b)—radical, and optionally substituted with up to 3 substituents selectedfrom R³. Examples of phenyl, pyridinyl, pyridazinyl or pyrazinyl areshown in Exhibit 2.

A wide variety of synthetic methods are known in the art to enablepreparation of aromatic and nonaromatic heterocyclic rings and ringsystems; for extensive reviews see the eight volume set of ComprehensiveHeterocyclic Chemistry, A. R. Katritzky and C. W. Rees editors-in-chief,Pergamon Press, Oxford, 1984 and the twelve volume set of ComprehensiveHeterocyclic Chemistry II, A. R. Katritzky, C. W. Rees and E. F. V.Scriven editors-in-chief, Pergamon Press, Oxford, 1996.

Compounds of this invention can exist as one or more stereoisomers.Stereoisomers are isomers of identical constitution but differing in thearrangement of their atoms in space and include enantiomers,diastereomers, cis-trans isomers (also known as geometric isomers) andatropisomers. Atropisomers result from restricted rotation about singlebonds where the rotational barrier is high enough to permit isolation ofthe isomeric species. One skilled in the art will appreciate that onestereoisomer may be more active and/or may exhibit beneficial effectswhen enriched relative to the other stereoisomer(s) or when separatedfrom the other stereoisomer(s). Additionally, the skilled artisan knowshow to separate, enrich, and/or to selectively prepare saidstereoisomers. For a comprehensive discussion of all aspects ofstereoisomerism, see Ernest L. Eliel and Samuel H. Wilen,Stereochemistry of Organic Compounds, John Wiley & Sons, 1994.

This invention comprises all stereoisomers, conformational isomers andmixtures thereof in all proportions as well as isotopic forms such asdeuterated compounds.

The compounds of the invention may be present as a mixture ofstereoisomers, or individual stereoisomers. For example, when R^(2a) andR^(2b) not the same, then Formula 1 possesses a chiral center at thecarbon atom to which R^(2a) and R^(2b) are bonded. The two enantiomersare depicted as Formula 1′ and Formula 1″ with the chiral centeridentified with an asterisk (*).

Molecular depictions drawn herein follow standard conventions fordepicting stereochemistry. To indicate stereoconfiguration, bonds risingfrom the plane of the drawing and towards the viewer are denoted bysolid wedges wherein the broad end of the wedge is attached to the atomrising from the plane of the drawing towards the viewer. Bonds goingbelow the plane of the drawing and away from the viewer are denoted bydashed wedges wherein the narrow end of the wedge is attached to theatom further away from the viewer. Constant width lines indicate bondswith a direction opposite or neutral relative to bonds shown with solidor dashed wedges; constant width lines also depict bonds in molecules orparts of molecules in which no particular stereoconfiguration isintended to be specified.

This invention comprises racemic mixtures, for example, equal amounts ofthe enantiomers of Formulae 1′ and 1″. In addition, this inventionincludes compounds that are enriched compared to the racemic mixture inan enantiomer of Formula 1. Also included are the essentially pureenantiomers of compounds of Formula 1, for example, Formula 1′ andFormula 1″.

When enantiomerically enriched, one enantiomer is present in greateramounts than the other, and the extent of enrichment can be defined byan expression of enantiomeric excess (“ee”), which is defined as(2x−1)·100%, where x is the mole fraction of the dominant enantiomer inthe mixture (e.g., an ee of 20% corresponds to a 60:40 ratio ofenantiomers).

Preferably the compositions of this invention have at least a 50%enantiomeric excess; more preferably at least a 75% enantiomeric excess;still more preferably at least a 90% enantiomeric excess; and the mostpreferably at least a 94% enantiomeric excess of the more active isomer.Of particular note are enantiomerically pure embodiments of the moreactive isomer.

Compounds of Formula 1 can comprise additional chiral centers. Forexample, substituents and other molecular constituents such as R¹ maythemselves contain chiral centers. This invention comprises racemicmixtures as well as enriched and essentially pure stereoconfigurationsat these additional chiral centers.

Compounds of this invention can exist as one or more conformationalisomers due to restricted rotation about the amide bond (e.g., AC(═Z)—N)in Formula 1. This invention comprises mixtures of conformationalisomers. In addition, this invention includes compounds that areenriched in one conformer relative to others.

One skilled in the art will appreciate that not all nitrogen containingheterocycles can form N-oxides since the nitrogen requires an availablelone pair for oxidation to the oxide; one skilled in the art willrecognize those nitrogen-containing heterocycles which can formN-oxides. One skilled in the art will also recognize that tertiaryamines can form N-oxides. Synthetic methods for the preparation ofN-oxides of heterocycles and tertiary amines are very well known by oneskilled in the art including the oxidation of heterocycles and tertiaryamines with peroxy acids such as peracetic and m-chloroperbenzoic acid(MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butylhydroperoxide, sodium perborate, and dioxiranes such asdimethyldioxirane. These methods for the preparation of N-oxides havebeen extensively described and reviewed in the literature, see forexample: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp748-750, S. V. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik inComprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boultonand A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keenein Advances in Heterocyclic Chemistry, vol. 43, pp 149-161, A. R.Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advancesin Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J.Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G.Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A.R. Katritzky and A. J. Boulton, Eds., Academic Press.

One skilled in the art recognizes that because in the environment andunder physiological conditions salts of chemical compounds are inequilibrium with their corresponding nonsalt forms, salts share thebiological utility of the nonsalt forms. Thus a wide variety of salts ofthe compounds of Formula 1 are useful for control of plant diseasescaused by fungal plant pathogens (i.e. are agriculturally suitable). Thesalts of the compounds of Formula 1 include acid-addition salts withinorganic or organic acids such as hydrobromic, hydrochloric, nitric,phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic,oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valericacids. When a compound of Formula 1 contains an acidic moiety such as acarboxylic acid or phenol, salts also include those formed with organicor inorganic bases such as pyridine, triethylamine or ammonia, oramides, hydrides, hydroxides or carbonates of sodium, potassium,lithium, calcium, magnesium or barium. Accordingly, the presentinvention comprises compounds selected from Formula 1, N-oxides andagriculturally suitable salts thereof.

Compounds selected from Formula 1, stereoisomers, tautomers, N-oxides,and salts thereof, typically exist in more than one form, and Formula 1thus includes all crystalline and non-crystalline forms of the compoundsthat Formula 1 represents. Non-crystalline forms include embodimentswhich are solids such as waxes and gums as well as embodiments which areliquids such as solutions and melts. Crystalline forms includeembodiments which represent essentially a single crystal type andembodiments which represent a mixture of polymorphs (i.e. differentcrystalline types). The term “polymorph” refers to a particularcrystalline form of a chemical compound that can crystallize indifferent crystalline forms, these forms having different arrangementsand/or conformations of the molecules in the crystal lattice. Althoughpolymorphs can have the same chemical composition, they can also differin composition due to the presence or absence of co-crystallized wateror other molecules, which can be weakly or strongly bound in thelattice. Polymorphs can differ in such chemical, physical and biologicalproperties as crystal shape, density, hardness, color, chemicalstability, melting point, hygroscopicity, suspensibility, dissolutionrate and biological availability. One skilled in the art will appreciatethat a polymorph of a compound represented by Formula 1 can exhibitbeneficial effects (e.g., suitability for preparation of usefulformulations, improved biological performance) relative to anotherpolymorph or a mixture of polymorphs of the same compound represented byFormula 1. Preparation and isolation of a particular polymorph of acompound represented by Formula 1 can be achieved by methods known tothose skilled in the art including, for example, crystallization usingselected solvents and temperatures. For a comprehensive discussion ofpolymorphism see R. Hilfiker, Ed., Polymorphism in the PharmaceuticalIndustry, Wiley-VCH, Weinheim, 2006.

Embodiments of the present invention as described in the Summary of theInvention include (where Formula 1 as used in the following Embodimentsincludes N-oxides and salts thereof):

Embodiment 1

-   -   A compound of Formula 1 wherein A is selected from the group        consisting of A-1, A-2, A-3 and A-4.

Embodiment 2

-   -   A compound of Formula 1 or Embodiment 1 wherein A is selected        from the group consisting of A-1, A-2 and A-3.

Embodiment 3

-   -   A compound of Formula 1 or any one of Embodiments 1 and 2        wherein A is selected from the group consisting of A-1 and A-2.

Embodiment 4

-   -   A compound of Formula 1 or any one of Embodiments 1 through 3        wherein A is A-2.

Embodiment 5

-   -   A compound of Formula 1 or any one of Embodiments 1 through 3        wherein A is A-1.

Embodiment 6

-   -   A compound of Formula 1 or any one of Embodiments 1 through 5        wherein Z is O.

Embodiment 7

-   -   A compound of Formula 1 or any one of Embodiments 1 through 6        wherein G is phenyl or pyridinyl substituted with Q meta or para        to the —C(R^(2a))R^(2b)— radical, and optionally substituted        with up to 2 substituents selected from R³.

Embodiment 8

-   -   A compound of Embodiment 7 wherein G is phenyl or pyridinyl        substituted with Q meta or para to the —C(R^(2a))R^(2b)—        radical, and optionally substituted with 1 substituent selected        from R³.

Embodiment 9

-   -   A compound of Embodiment 8 wherein G is phenyl substituted with        Q meta or para to the —C(R^(2a))R^(2b)— radical, and optionally        substituted with 1 substituent selected from R³.

Embodiment 10

-   -   A compound of Embodiment 9 wherein G is phenyl substituted with        Q para to the —C(R^(2a))R^(2b)— radical (i.e. unsubstituted with        R³).

Embodiment 10a

-   -   A compound of Embodiment 9 wherein G is phenyl substituted with        Q para to the —C(R^(2a))R^(2b)— radical, and unsubstituted with        R³.

Embodiment 11

-   -   A compound of Embodiment 8 wherein G is pyridinyl substituted        with Q meta or para to the —C(R^(2a))R^(2b)— radical, and        optionally substituted with 1 substituent selected from R³.

Embodiment 12

-   -   A compound of Embodiment 11 wherein G is pyridinyl substituted        with Q para to the —C(R^(2a))R^(2b)— radical (i.e. unsubstituted        with R³).

Embodiment 13

-   -   A compound of Formula 1 or any one of Embodiments 1 through 12        wherein R¹ is C₃-C₄ cycloalkyl; or a 4- to 5-membered ring        containing ring members selected from carbon atoms, 1O atom and        1S atom.

Embodiment 14

-   -   A compound of Embodiment 13 wherein R¹ is cyclopropyl; or a        4-membered ring containing ring members selected from carbon        atoms, 1O atom and 1S atom.

Embodiment 15

-   -   A compound of Embodiment 14 wherein R¹ is cyclopropyl,        3-oxetanyl or 3-thietanyl.

Embodiment 16

-   -   A compound of Embodiment 15 wherein R¹ is cyclopropyl.

Embodiment 17

-   -   A compound of Formula 1 or any one of Embodiments 1 through 16        wherein R^(2a) is H, CH₃, CF₃ or CHF₂.

Embodiment 18

-   -   A compound of Embodiment 17 wherein R^(2a) is H, F or CH₃.

Embodiment 19

-   -   A compound of Embodiment 18 wherein R^(2a) is H.

Embodiment 20

-   -   A compound of Embodiment 18 wherein R^(2a) is F.

Embodiment 21

-   -   A compound of Embodiment 18 wherein R^(2a) is CH₃.

Embodiment 22

-   -   A compound of Formula 1 or any one of Embodiments 1 through 21        wherein R^(2b) is H or CH₃.

Embodiment 23

-   -   A compound of Embodiment 22 wherein R^(2b) is H.

Embodiment 24

-   -   A compound of Formula 1 or any one of Embodiments 1 through 16        wherein when R^(2a) and R^(2b) are taken together, they are        taken together as C₂ or C₃ alkanediyl.

Embodiment 25

-   -   A compound of Embodiment 24 wherein R^(2a) and R^(2b) are taken        together as C₂ alkanediyl (i.e. R^(2a) and R^(2b) are taken        together along with the carbon to which they are attached to        form a cyclopropyl ring).

Embodiment 26

-   -   A compound of Formula 1 or any one of Embodiments 1 through 9,        11 or 13 through 25 wherein R³ is halogen, cyano, C₁-C₅ alkyl,        C₁-C₅ haloalkyl, C₁-C₅ alkoxy, C₁-C₅ haloalkoxy, C₂-C₅        alkoxyalkyl or C₃-C₅ cycloalkyl.

Embodiment 27

-   -   A compound of Embodiment 26 wherein R³ is halogen, CH₃, CF₃,        CHF₂, OCH₃, OCF₃, CH₂CH₂OCH₃ or cyclopropyl.

Embodiment 28

-   -   A compound of Embodiment 27 wherein R³ is Cl, Br, CH₃, CF₃,        CHF₂, OCH₃ or cyclopropyl.

Embodiment 29

-   -   A compound of Embodiment 28 wherein R³ is Cl.

Embodiment 30

-   -   A compound of Formula 1 or any one of Embodiments 1 through 3 or        5 through 29 wherein R⁴ is halogen, C₁-C₂ alkyl or C₁-C₂        haloalkyl.

Embodiment 31

-   -   A compound of Embodiment 30 wherein R⁴ is halogen, CH₃ or C₁        haloalkyl.

Embodiment 32

-   -   A compound of Embodiment 31 wherein R⁴ is F, Cl, Br, CH₃, CHF₂        or CF₃.

Embodiment 33

-   -   A compound of Embodiment 32 wherein R⁴ is CHF₂.

Embodiment 34

-   -   A compound of Formula 1 or any one of Embodiments 1 through 3 or        5 through 33 wherein R⁵ is H, halogen, C₁-C₂ alkyl or C₁-C₂        haloalkyl.

Embodiment 35

-   -   A compound of Embodiment 34 wherein R⁵ is H, halogen, CH₃ or C₁        haloalkyl.

Embodiment 36

-   -   A compound of Embodiment 35 wherein R⁵ is H, F, Cl, Br, CH₃,        CHF₂ or CF₃.

Embodiment 37

-   -   A compound of Embodiment 36 wherein R⁵ is F or Cl.

Embodiment 38

-   -   A compound of Formula 1 or any one of Embodiments 1 through 3 or        5 through 37 wherein R⁶ is CH₃.

Embodiment 39

-   -   A compound of Formula 1 or any one of Embodiments 1 through 4 or        6 through 29 wherein R⁷ is halogen, C₁-C₂ alkyl or C₁-C₂        haloalkyl.

Embodiment 40

-   -   A compound of Embodiment 39 wherein R⁷ is halogen, CH₃ or C₁        haloalkyl.

Embodiment 41

-   -   A compound of Embodiment 40 wherein R⁷ is F, Cl, Br, CH₃, CHF₂        or CF₃.

Embodiment 42

-   -   A compound of Formula 1 or any one of Embodiments 1 through 4 or        6 through 29 or 39 through 41 wherein R⁸ is H or CH₃.

Embodiment 43

-   -   A compound of Formula 1 or any one of Embodiments 1, 2 or 6        through 29 wherein R⁹ is halogen, C₁-C₂ alkyl or C₁-C₂        haloalkyl.

Embodiment 44

-   -   A compound of Embodiment 43 wherein R⁹ is halogen, CH₃ or C₁        haloalkyl.

Embodiment 45

-   -   A compound of Embodiment 44 wherein R⁹ is F, Cl, Br, CHF₂ or        CF₃.

Embodiment 46

-   -   A compound of Formula 1 or Embodiment 1 wherein R¹⁰ is F, Cl,        Br, CH₃, CHF₂ or CF₃.

Embodiment 47

-   -   A compound of Formula 1 wherein R¹¹ is F, Cl, Br, CH₃, CHF₂ or        CF₃.

Embodiment 48

-   -   A compound of Formula 1 or Embodiment 47 wherein m is 0 or 2.

Embodiment 49

-   -   A compound of Formula 1 or any one of Embodiments 1 through 48        wherein the heterocyclic ring Q contains at least one nitrogen        atom ring member.

Embodiment 50

-   -   A compound of Embodiment 49 wherein the heterocyclic ring Q        contains two nitrogen atom ring members.

Embodiment 51

-   -   A compound of Formula 1 or any one of Embodiments 1 through 50        wherein the heterocyclic ring Q is fully unsaturated (i.e. is        heteroaromatic).

Embodiment 52

-   -   A compound of Formula 1 or any one of Embodiments 1 through 51        wherein the heterocyclic ring Q is selected from furan,        thiophene, pyrrole, oxazole, thiazole, imidazole, isoxazole,        isothiazole, pyrazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole,        1,3,4-oxadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole,        1,3,4-thiadiazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole,        4,5-dihydroisoxazole and 4,5-dihydropyrazole.

Embodiment 53

-   -   A compound of Embodiment 52 wherein the heterocyclic ring Q is        selected from pyrazole.

Embodiment 54

-   -   A compound of Embodiment 51 wherein Q is selected from Q-1        through Q-21 depicted in Exhibit 3.

wherein

-   -   R¹² is bonded to a ring member distal relative to the ring        member connecting the Q ring to the remainder of Formula 1, and        independently selected from R^(12c) on carbon atom ring members        and R^(12n) on nitrogen atom ring members;    -   each R¹³ is independently selected from R^(13c) on carbon atom        ring members and R^(13n) on nitrogen atom ring members;    -   each x is independently 0 or 1;    -   each y is independently 0, 1 or 2; and    -   each z is independently 0, 1, 2 or 3.

Embodiment 55

-   -   A compound of Embodiment 54 wherein Q is selected from Q-1        through Q-19.

Embodiment 56

-   -   A compound of Embodiment 55 wherein Q is selected from

Embodiment 57

-   -   A compound of Embodiment 56 wherein Q is selected from Q-9A and        Q-9B.

Embodiment 58

-   -   A compound of Embodiment 57 wherein Q is Q-9A.

Embodiment 59

-   -   A compound of any one of Embodiments 56 through 58 wherein y is        0 or 1.

Embodiment 60

-   -   A compound of Formula 1 or any one of Embodiments 1 through 59        wherein each R^(12c) is independently halogen, cyano, C₁-C₂        alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy.

Embodiment 61

-   -   A compound of Embodiment 60 wherein each R^(12c) is        independently halogen, CH₃ or C₁ haloalkyl.

Embodiment 62

-   -   A compound of Embodiment 61 wherein each R^(12c) is        independently F, Cl, Br, CH₃, CHF₂ or CF₃.

Embodiment 63

-   -   A compound of Embodiment 62 wherein each R^(12c) is        independently CF₃.

Embodiment 64

-   -   A compound of Formula 1 or any one of Embodiments 1 through 63        wherein each R^(12n) is independently C₁-C₂ alkyl or C₁-C₂        haloalkyl.

Embodiment 65

-   -   A compound of Embodiment 64 wherein each R^(12n) is C₁-C₂ alkyl.

Embodiment 66

-   -   A compound of Embodiment 65 wherein each R^(12n) is CH₃.

Embodiment 67

-   -   A compound of Formula 1 or any one of Embodiments 1 through 66        wherein each R^(13c) is independently halogen, C₁-C₂ alkyl,        C₁-C₂ haloalkyl or C₁-C₂ alkoxy.

Embodiment 68

-   -   A compound of Embodiment 67 wherein each R^(13c) is        independently halogen, CH₃ or C₁ haloalkyl.

Embodiment 69

-   -   A compound of Embodiment 68 wherein each R^(13c) is        independently F, Cl, Br, CH₃, CHF₂ or CF₃.

Embodiment 70

-   -   A compound of Formula 1 or any one of Embodiments 1 through 69        wherein each R^(13n) is independently C₁-C₂ alkyl or C₁-C₂        haloalkyl.

Embodiment 71

-   -   A compound of Embodiment 70 wherein each R^(13n) is C₁-C₂ alkyl.

Embodiment 72

-   -   A compound of Embodiment 71 wherein each R^(13n) is CH₃.

Embodiment 73

-   -   A compound of Formula 1 or any one of Embodiments 1 through 72        wherein each R¹⁴, R^(15c)c, R¹⁶ and R^(17c) is independently        halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl or C₁-C₂ alkoxy.

Embodiment 74

-   -   A compound of Embodiment 73 wherein each R¹⁴, R^(15c), R¹⁶ and        R^(17c) is independently halogen, CH₃ or C₁ haloalkyl.

Embodiment 75

-   -   A compound of Embodiment 74 wherein each R¹⁴, R^(15c), R¹⁶ and        R^(17c) is independently F, Cl, Br, CH₃, CHF₂ or CF₃.

Embodiment 76

-   -   A compound of Formula 1 or any one of Embodiments 1 through 75        wherein each R^(15n) and R^(17n) is independently C₁-C₂ alkyl or        C₁-C₂ haloalkyl.

Embodiment 77

-   -   A compound of Embodiment 76 wherein each R^(15n) and R^(17n) is        independently C₁-C₂ alkyl.

Embodiment 78

-   -   A compound of Embodiment 77 wherein each R^(15n) and R^(17n) is        CH₃.

Embodiments of this invention, including Embodiments 1-78 above as wellas any other embodiments described herein, can be combined in anymanner, and the descriptions of variables in the embodiments pertain notonly to the compounds of Formula 1 but also to the starting compoundsand intermediate compounds useful for preparing the compounds ofFormula 1. In addition, embodiments of this invention, includingEmbodiments 1-78 above as well as any other embodiments describedherein, and any combination thereof, pertain to the compositions andmethods of the present invention.

Combinations of Embodiments 1-78 are illustrated by:

Embodiment A

-   -   A compound of Formula 1 wherein    -   Z is O;    -   R¹ is C₃-C₄ cycloalkyl; or a 4- to 5-membered ring containing        ring members selected from carbon atoms, 1O atom and 1S atom;    -   R^(2a) is H, CH₃, CF₃ or CHF₂;    -   R^(2b) is H or CH₃; or    -   R^(2a) and R^(2b) are taken together as C₂ or C₃ alkanediyl;    -   G is phenyl or pyridinyl substituted with Q meta or para to the        —C(R^(2a))R^(2b)— radical, and optionally substituted with up to        2 substituents selected from R³;    -   R³ halogen, cyano, C₁-C₅ alkyl, C₁-C₅ haloalkyl, C₁-C₅ alkoxy,        C₁-C₅ haloalkoxy, C₂-C₅ alkoxyalkyl, C₃-C₅ cycloalkyl;    -   R⁴ is halogen, C₁-C₂ alkyl or C₁-C₂ haloalkyl;    -   R⁵ is H, halogen, C₁-C₂ alkyl or C₁-C₂ haloalkyl;    -   R⁶ is CH₃;    -   R⁷ is halogen, C₁-C₂ alkyl or C₁-C₂ haloalkyl;    -   R⁸ is H or CH₃;    -   R⁹ is halogen, C₁-C₂ alkyl or C₁-C₂ haloalkyl;    -   R¹⁰ is F, Cl, Br, CH₃, CHF₂ or CF₃;    -   R¹¹ is F, Cl, Br, CH₃, CHF₂ or CF₃;    -   Q is selected from Q-1 through Q-21 (as depicted in Embodiment        54);    -   each R^(12c) is independently halogen, cyano, C₁-C₂ alkyl, C₁-C₂        haloalkyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy;    -   each R^(12n) is independently C₁-C₂ alkyl or C₁-C₂ haloalkyl;    -   each R^(13c) is independently halogen, C₁-C₂ alkyl, C₁-C₂        haloalkyl or C₁-C₂ alkoxy;    -   each R^(13n) is independently C₁-C₂ alkyl or C₁-C₂ haloalkyl;    -   each R¹⁴, R^(15c), R¹⁶ and R^(17c) is independently halogen, CH₃        or C₁ haloalkyl; and    -   R^(15n) and R^(17n) is independently C₁-C₂ alkyl or C₁-C₂        haloalkyl.

Embodiment B

-   -   A compound of Embodiment A wherein    -   A is selected from the group consisting of A-1, A-2, A-3 and        A-4;    -   R¹ is cyclopropyl; or a 4-membered ring containing ring members        selected from carbon atoms, 1O atom and 1S atom;    -   R^(2a) is H, F or CH₃;    -   R^(2b) is H; or    -   R^(2a) and R^(2b) are taken together as C₂ alkanediyl;    -   G is phenyl or pyridinyl substituted with Q meta or para to the        —C(R^(2a))R^(2b)— radical, and optionally substituted with 1        substituent selected from R³;    -   R³ is halogen, CH₃, CF₃, CHF₂, OCH₃, OCF₃, CH₂CH₂OCH₃ or        cyclopropyl;    -   R⁴ is halogen, CH₃ or C₁ haloalkyl;    -   R⁵ is H, F, Cl, Br, CH₃, CHF₂ or CF₃;    -   R⁷ is halogen, CH₃ or C₁ haloalkyl;    -   R⁹ is F, Cl, Br, CHF₂ or CF₃;    -   Q is selected from Q-1 through Q-19;    -   R^(12c) is independently halogen, CH₃ or C₁ haloalkyl;    -   R^(12n) is C₁-C₂ alkyl;    -   each R^(13c) is independently halogen, CH₃ or C₁ haloalkyl;    -   each R^(13n) is C₁-C₂ alkyl;    -   each R¹⁴, R^(15c), R¹⁶ and R^(17c) is independently F, Cl, Br,        CH₃, CHF₂ or CF₃; and    -   each R^(15n) and R^(17n) is independently C₁-C₂ alkyl.

Embodiment C

-   -   A compound of Embodiment B wherein    -   A is selected from the group consisting of A-1, A-2 and A-3;    -   R¹ is cyclopropyl, 3-oxetanyl or 3-thietanyl;    -   G is phenyl substituted with Q meta or para to the        —C(R^(2a))R^(2b)— radical, and optionally substituted with 1        substituent selected from R³;    -   R³ is Cl, Br, CH₃, CF₃, CHF₂, OCH₃ or cyclopropyl;    -   R⁴ is F, Cl, Br, CH₃, CHF₂ or CF₃;    -   R⁵ is F or Cl;    -   R⁷ is F, Cl, Br, CH₃, CHF₂ or CF₃;    -   R⁹ is F, Cl, Br, CHF₂ or CF₃;    -   Q is selected from Q-9A, Q-9B and Q-9C (as depicted in        Embodiment 56);    -   each R^(12c) is independently F, Cl, Br, CH₃, CHF₂ or CF₃;    -   each R^(12n) is CH₃;    -   each R^(13c) is independently F, Cl, Br, CH₃, CHF₂ or CF₃;    -   each R^(13n) is CH₃; and    -   each R^(15n) and R^(17n) is CH₃.

Embodiment D

-   -   A compound of Embodiment A wherein    -   A is selected from the group consisting of A-1 and A-2;    -   R¹ is cyclopropyl;    -   G is phenyl substituted with Q para to the —C(R^(2a))R^(2b)—        radical, and unsubstituted with R³;    -   R⁴ is CHF₂;    -   Q is selected from Q-9A and Q-9B; and    -   R^(12c) is CF₃.

Embodiment E

-   -   A compound of Embodiment B wherein    -   A is A-1;    -   R¹ is cyclopropyl;    -   G is pyridinyl substituted with Q meta or para to the        —C(R^(2a))R^(2b)— radical, and optionally substituted with 1        substituent selected from R³;    -   R³ is Cl;    -   R⁴ is CHF₂;    -   Q is Q-9A; and    -   R^(12c) is CF₃.

Specific embodiments include compounds of Formula 1 selected from thegroup consisting of:

-   N-[[2-chloro-4-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl]methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide    (Compound 12); and-   N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[3-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl]methyl]-1H-pyrazole-4-carboxamide    (Compound 3).

This invention also includes a compound of Formula 1 wherein R³ ishalogen, nitro, cyano, C₁-C₅ alkyl, C₁-C₅ haloalkyl, C₁-C₅ alkoxy, C₁-C₅haloalkoxy, C₂-C₅ alkoxyalkyl, C₃-C₅ cycloalkyl, C₂-C₅ alkoxycarbonyl orC₃-C₁₂ trialkylsilyl. This invention provides a fungicidal compositioncomprising a compound of Formula 1 (including all stereoisomers,N-oxides, and salts thereof), and at least one other fungicide. Of noteas embodiments of such compositions are compositions comprising acompound corresponding to any of the compound embodiments describedabove.

This invention provides a fungicidal composition comprising a compoundof Formula 1 (including all stereoisomers, N-oxides, and salts thereof)(i.e. in a fungicidally effective amount), and at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents. Of note as embodiments of suchcompositions are compositions comprising a compound corresponding to anyof the compound embodiments described above.

This invention provides a method for controlling plant diseases causedby fungal plant pathogens comprising applying to the plant or portionthereof, or to the plant seed, a fungicidally effective amount of acompound of Formula 1 (including all stereoisomers, N-oxides, and saltsthereof). Of note as embodiment of such methods are methods comprisingapplying a fungicidally effective amount of a compound corresponding toany of the compound embodiments describe above. Of particular notes areembodiments where the compounds are applied as compositions of thisinvention.

One or more of the following methods and variations as described inSchemes 1-11 can be used to prepare the compounds of Formula 1. Thedefinitions of A, R¹, R^(2a), R^(2b), G, Q, and Z in the compounds ofFormulae 1-21 below are as defined above in the Summary of the Inventionunless otherwise noted. Compounds of Formulae 1a-1c are various subsetsof a compound of Formula 1, and all substituents for Formulae 1a-1c areas defined above for a compound of Formula 1. Compounds of Formulae2a-2b are various subsets of a compound of Formula 2, and allsubstituents for Formulae 2a-2b are as defined herein for a compound ofFormula 2. Compounds of Formulae 7a-7c are various subsets of a compoundof Formula 7, and all substituents for Formulae 7a-7c are as definedherein for a compound Formula 7. Compounds of Formulae 9a-9b are varioussubsets of a compound of Formula 9, and all substituents for Formulae9a-9b are as defined hererin for a compound of Formula 9.

As shown in Scheme 1, a compound of Formula 1b (i.e. Formula 1 wherein Zis sulfur) may be prepared from a compound of Formula 1a (i.e. Formula 1wherein Z is oxygen) by treatment with Lawesson's reagent, P₂S₅, orP₄S₁₀. Thioamide formation reactions of this type are typicallyconducted in an aprotic solvent such as toluene or p-dioxane at elevatedtemperatures between 40° C. and the boiling point of the solvent.Reactions of this type are well known in the literature; see, forexample, March and Smith, March's Advanced Organic Chemistry, 5^(th)ed., John Wiley & Sons, Inc., New York, 2001, Chapter 16.

As shown in Scheme 2, a compound of Formula 1c (i.e. a compound ofFormula 1 wherein Z is oxygen; and Q is a nitrogen-linked heterocycledenoted by Q^(N) positioned meta or para to the —C(R^(2a))R^(2b)—radical on the G ring) may be prepared by nucleophilic aromaticsubstitution by reaction of a compound of Formula 2a (i.e. a compound ofFormula 2 wherein L is a phenyl, pyridinyl, pyridazinyl or pyrazinylgroup) with a heterocycle of Formula 3 wherein a hydrogen atom is bondedto a ring nitrogen. These substitution reactions are typically conductedin a polar aprotic solvent such as N,N-dimethylformamide ordimethylsulfoxide in the presence of an inorganic base such as potassiumor cesium carbonate at temperatures between ambient and the boilingpoint of the solvent. These types of reactions are well documented inthe literature (see, for example, March and Smith, March's AdvancedOrganic Chemistry, 5th ed., John Wiley & Sons, Inc., New York, 2001,Chapter 13). Heterocycles of Formula 3 are commercially available or maybe prepared by methods well known in the art.

As also shown in Scheme 2, a compound of Formula 1c may be prepared bycopper-catalyzed Buchwald-Hartwig coupling of a compound of Formula 2bwith a heterocycle of Formula 3 wherein a ring nitrogen is bonded to ahydrogen atom. These coupling reactions are typically conducted in anaprotic solvent such as p-dioxane, 1,2-diethoxyethane or toluene in thepresence of a suitable ligand, a copper(I) salt such as CuI or CuBr, anda base such as sodium or potassium carbonate. Typical ligands aretrans-N,N′-dimethyl-1,2-diaminocyclohexane and phenanthroline, andtypical reaction temperatures range from ambient temperature to reflux.Conditions for this reaction are well known in the literature (seeChemical Science 2010, 1, 13-31, Chemical Reviews 2008, 108(8),3054-3131, and references cited therein).

As also shown in Scheme 2, a compound of Formula 1d (i.e. Formula 1wherein Z is oxygen; and Q is a carbon-linked heterocycle denoted byQ^(C) positioned meta or para to the —C(R^(2a))R^(2b)— radical on the Gring) can be prepared by Suzuki coupling reaction. A compound of Formula2b (i.e. a compound of Formula 2 wherein L is a phenyl, pyridinyl,pyridazinyl, or pyrazinyl group) may be coupled with a boronic acid orester of Formula 4, wherein a ring carbon is bonded to boron, in thepresence of Pd(0) or Pd(II) salts, a suitable ligand, and a base.Suitable bases for this transformation are potassium carbonate or cesiumcarbonate. Pd(II) salts such as Pd(OAc)₂ or PdCl₂ are used inconjunction with ligands such as triphenylphosphine or1,1′-bis(diphenylphosphino)ferrocene (dppf). Conditions for Suzukicouplings are well documented in the literature (see, for example,Angewandte Chemie, Int. Ed. 2006, 45, 3484). A boronic acid or ester ofFormula 4 is commercially available or may be prepared from thecorresponding halides or trifluoromethanesulfonates by methods known inthe literature (see, for example, J. Org. Chem. 1995, 60, 7508).

Alternatively, as shown in Scheme 3, a compound of Formula 1c may beprepared from a boron intermediate of Formula 5 using Chan-Lamconditions by coupling with a nitrogen heterocycle of Formula 3 in thepresence of a Cu(II) salt, oxygen, and a base at temperatures rangingfrom ambient to the reflux temperature of the solvent. Examples ofCu(II) salts which may be used are Cu(OAc)₂, CuBr₂, and CuI₂. Suitablebases for this reaction type include pyridine, quinolone, andtriethylamine, and suitable solvents include dichloromethane,chloroform, diethyl ether, and tetrahydrofuran. For representativeconditions see Tetrahedron Letters 1998, 39, 2941, Angewandte Chemie,Int. Ed. 2003, 42, 5400, and references therein.

As also shown in Scheme 3, a compound of Formula 1d may be prepared viaSuzuki reaction by coupling of a boronic acid or ester of Formula 5 witha heterocycle of Formula 6 wherein X² is bonded to a ring carbon.Conditions for carrying out such couplings are analogous to the Suzukiconditions described in Scheme 2. A compound of Formula 6 iscommercially available or may readily be prepared by methods describedin the literature.

A compound of Formula 5 may be prepared from a compound of Formula 2busing the methods cited for the preparation of a compound of Formula 4in Scheme 2.

As shown in Scheme 4, a compound of Formula 2 may be prepared by theacylation of amine derivatives of a compound of Formula 7 with acompound of Formula 8. These types of acylations are well documented inthe literature (see, for example, March and Smith, March's AdvancedOrganic Chemistry, 5th ed., John Wiley & Sons, Inc., New York, 2001,Chapter 10).

As shown in Scheme 5, a compound of Formula 7a (i.e. a compound ofFormula 7 wherein R¹ is cyclopropyl) may be prepared by the reaction ofa primary amine derivative of Formula 9 with commercially availablecyclopropanone ethyl trimethylsilyl acetal 10 in acetic acid/methanol inthe presence of sodium cyanoborohydride (see, for example, PCT PatentPublication WO2012/22265). A compound of Formula 9 is commerciallyavailable or may readily be prepared by methods described in theliterature.

As shown in Scheme 6, a compound of Formula 7b (i.e. a compound ofFormula 7 wherein R¹ is cyclobutyl, cyclopentyl, or a 4- to 6-memberedring containing ring members selected from carbon atoms, 1O atom and 1Satom) may be prepared by condensation of a primary amine of Formula 9with a ketone of Formula 11 followed by treatment with a reducing agentsuch as sodium borohydride, sodium cyanoborohydride, or sodiumtriacetoxyborohydride. For representative conditions, see J. Med. Chem.2005, 48(4), 1169 and PCT Patent Publication WO 2012/66070.

As shown in Scheme 7, an amine of Formula 7 or Formula 7c (i.e. acompound of Formula 7 wherein R^(2b) is H) may be prepared from a ketoneof Formula 12. Condensation of an amine of Formula 13 with a ketone ofFormula 12 results in the formation of imines of Formula 14.Condensation reactions of this type are well known in the literature(see March and Smith, March's Advanced Organic Chemistry, 5th ed., JohnWiley & Sons, Inc., New York, 2001, Chapter 16). Treatment of an imineof Formula 14 with a reducing agent provides amines of Formula 7c.Typical reducing agents used in these reactions include sodiumborohydride, sodium cyanoborohydride, and sodium triacetoxyborohydride,and typical solvents are methanol, ethanol, acetonitrile, ortetrahydrofuran. The transformation of a compound of Formula 12 to acompound of Formula 7c is often done in a single reaction pot. Forrepresentative conditions, see US Patent Publications US2005/58301 andUS2008/275085. A dialkylated or haloalkylated compound of Formula 7 maybe obtained by treatment of an imine of Formula 14 with an alkyl- orhaloalkyl-metal species of Formula 15. Typical reaction temperatures forthis alkylation reaction range from −78° C. to 60° C. and typicalsolvents include tetrahydrofuran, acetonitrile and diethyl ether. Forrepresentative conditions, see US2012/59162 and Tetrahedron 2011,67(14), 2670. A ketone of Formula 12, an amine of Formula 13, and ametal reagent of Formula 15 are commercially available or may readily beprepared by methods described in the literature.

As shown in Scheme 8, a compound of Formula 9a (i.e. a compound ofFormula 9 wherein R^(2a) and R^(2b) are both H) may be prepared by thereduction of a corresponding nitrile compound of Formula 16. The nitrilereduction may be performed via a number of methods, including the use ofhydrogen/palladium on carbon, nickel(II) chloride/sodium borohydride orborane, which are well documented in the literature. See, for example,Smith, M. B., Organic Synthesis, 2^(nd) ed., McGraw-Hill Companies,Inc., 2002, Chapter 4, and references cited therein. A compound ofFormula 16 is commercially available or may readily be prepared bymethods described in the literature.

A compound of Formula 9b (i.e. a compound of Formula 9 wherein R^(2a) isF and R^(2b) is F or H) may be prepared as shown in Scheme 9. Treatmentof a bromide of Formula 17 with silver nitrite in a solvent such asdiethyl ether at temperatures from about 0° C. to ambient temperaturemay provide a nitro compound of Formula 18. For representativeconditions, see US2012/165343. A compound of Formula 19 may be preparedby treatment of a compound of Formula 18 with a base such as potassiumhydroxide, tetrabutylammonium hydroxide, sodium hydride or ammoniumacetate and an electrophilic fluorinating reagent such as Selectfluor™(1-chloromethyl-4-fluoro-1,4-diazoniabicyclo-[2.2.2]octanebis(tetrafluoroborate)) in solvents such as N,N-dimethylformamide,acetonitrile, dichloromethane or methanol at temperatures around 0° C.to ambient temperature. One skilled in the art will recognize that theseconditions may be modulated to obtain the mono-fluorinated product (i.e.a compound of Formula 19 wherein R⁵³ is H) or the di-fluorinated product(i.e. a compound of Formula 19 wherein R⁵³ is F). In cases where productmixtures are produced, the desired product may be isolated usingseparation techniques well known in the art. For representativeconditions see Tetrahedron Letters 2005, 46, 4905 and TetrahedronLetters 2006, 47, 4519. An amino compound of Formula 9b may be preparedvia the reduction of a nitro compound of Formula 19 using Fe, Zn, ortin(II) chloride in aqueous acidic media at temperatures ranging fromambient temperature to reflux. Alcohol co-solvents such as methanol,ethanol, and isopropanol may also be employed. Acids such ashydrochloric, hydrobromic, and acetic, or ammonium chloride, aretypically employed. Conditions for such reductions may be found in J.Med. Chem. 2012, 55(3), 1021. Alternatively, hydrogenation conditionssuch as the use of Raney nickel under an atmosphere of hydrogen may beutilized to prepare a compound of Formula 9b. This type of hydrogenationis typically conducted in a solvent such as ethanol. For representativeconditions, see US2012/259111. A compound of Formula 17 is commerciallyavailable or may readily be prepared by methods described in theliterature.

As shown in Scheme 10, a compound of Formula 1a can be prepared bycoupling of an amine of Formula 20 with an acid derivative of Formula 8according to the methods described for the preparation of a compound ofFormula 2 in Scheme 4.

As shown in Scheme 11, a compound of Formula 20 may be prepared eitherfrom a compound of Formula 7 using the coupling methods described inScheme 2 with reagents of compounds of Formulae 3 or 4, or from a boronderivative of Formula 21 using the coupling methods described in Scheme3 with a compound of Formulae 3 or 6. A compound of Formula 21 can beprepared from a compound of Formula 7 using methods cited for thepreparation of 4 in Scheme 2.

It is recognized that some reagents and reaction conditions describedabove for preparing a compound of Formula 1 may not be compatible withcertain functionalities present in the intermediates. In theseinstances, the incorporation of protection/deprotection sequences orfunctional group interconversions into the synthesis will aid inobtaining the desired products. The use and choice of the protectinggroups will be apparent to one skilled in chemical synthesis (see, forexample, Greene, T. W.; Wuts, P. G. M. Protective Groups in OrganicSynthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art willrecognize that, in some cases, after the introduction of a given reagentas it is depicted in any individual scheme, it may be necessary toperform additional routine synthetic steps not described in detail tocomplete the synthesis of compounds of Formula 1. One skilled in the artwill also recognize that it may be necessary to perform a combination ofthe steps illustrated in the above schemes in an order other than thatimplied by the particular sequence presented to prepare the compounds ofFormula 1.

One skilled in the art will also recognize that compounds of Formula 1and the intermediates described herein can be subjected to variouselectrophilic, nucleophilic, radical, organometallic, oxidation, andreduction reactions to add substituents or modify existing substituents.

Without further elaboration, it is believed that one skilled in the artusing the preceding description can utilize the present invention to itsfullest extent. The following Examples are, therefore, to be construedas merely illustrative, and not limiting of the disclosure in any waywhatsoever. Steps in the following Examples illustrate a procedure foreach step in an overall synthetic transformation, and the startingmaterial for each step may not have necessarily been prepared by aparticular preparative run whose procedure is described in otherExamples or Steps. Percentages are by weight except for chromatographicsolvent mixtures or where otherwise indicated. Parts and percentages forchromatographic solvent mixtures are by volume unless otherwiseindicated. ¹H NMR spectra are reported in ppm downfield fromtetramethylsilane in CDCl₃ unless otherwise noted; “s” means singlet,“d” means doublet, “t” means triplet, “m” means multiplet, “dd” meansdoublet of doublets, “dt” means doublet of triplets, “br s” means broadsinglet.

Example 1 Preparation ofN-cyclopropyl-3-(difluoromethyl)-1-methyl-N-[1-[6-[3-(trifluoromethyl)-1H-pyrazol-1-yl]-3-pyridinyl]ethyl]-1H-pyrazole-4-carboxamide(Compound 1) Step A: Preparation of6-chloro-N-cyclopropyl-α-methyl-3-pyridinemethanamine

A stirred mixture of cyclopropylamine (2.1 g, 37.0 mmol) and 2 Åmolecular sieves (2.0 g) in methanol (25 mL) was cooled to 0° C. andtreated successively with glacial acetic acid (2.75 mL) and1-(6-chloro-3-pyridinyl)ethanone (2.88 g, 18.5 mmol). External coolingwas removed and the mixture was heated to reflux for 3 h and thenallowed to cool to ambient temperature. A solution of sodiumcyanoborohydride (1.73 g, 46.3 mmol) in methanol (5 mL) was addeddropwise, and the reaction mixture was heated to reflux for anadditional 3 h. The cooled reaction mixture was concentrated underreduced pressure, and the resulting residue purified by silica gelchromatography eluting with 20 to 50% ethyl acetate in hexanes to yieldthe title compound (1.61 g).

¹H NMR δ 8.32 (m, 1H), 7.65 (m, 1H), 7.28 (d, 1H), 3.91 (m, 1H), 1.96(m, 1H), 1.74 (br s, 1H), 1.36 (d, 3H), 0.38 (m, 3H), 0.20 (m, 1H).

Step B: Preparation ofN-[1-(6-chloro-3-pyridinyl)ethyl]-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide

A mixture of 3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid(0.25 g, 1.42 mmol) and thionyl chloride (5 mL) was heated to reflux for1 h. The cooled reaction mixture was concentrated under reduced pressureand the resulting residue was twice diluted with toluene andconcentrated under reduced pressure. The residual3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carbonyl chloride was taken upin dichloromethane (5 mL) and treated dropwise at room temperature witha mixture of 6-chloro-N-cyclopropyl-a-methyl-3-pyridinemethanamine (i.e.the product of Step A, 0.23 g, 1.18 mmol) and triethylamine (0.12 g,1.18 mmol) in dichloromethane. The reaction mixture was stirredovernight at ambient temperature, and then partitioned between 1Nhydrochloric acid and dichloromethane. The organic phase was separatedand the aqueous phase extracted again with dichloromethane. The combinedorganic phases were dried (MgSO₄) and concentrated under reducedpressure. The residue was chromatographed on silica gel eluting with 30to 100% ethyl acetate in hexanes to yield the title compound (0.27 g).

¹H NMR δ 8.39 (m, 1H), 7.65 (m, 2H), 7.28 (d, 1H), 7.01 (t, 1H), 5.68(m, 1H), 3.96 (s, 3H), 2.62 (m, 1H), 1.79 (d, 3H), 0.64 (m, 2H), 0.52(m, 1H), 0.35 (m, 1H).

Step C: Preparation ofN-cyclopropyl-3-(difluoromethyl)-1-methyl-N-[1-[6-[3-(trifluoromethyl)-1H-pyrazol-1-yl]-3-pyridinyl]ethyl]-1H-pyrazole-4-carboxamide

A mixture ofN-[1-(6-chloro-3-pyridinyl)ethyl]-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide(i.e. the product of Step B, 0.08 g, 0.23 mmol),3-(trifluoromethyl)-1H-pyrazole (0.02 g, 0.15 mmol),trans-N,N-dimethyl-1,2-diaminocyclohexane (0.01 g, 0.07 mmol), copper(I)iodide (0.01 g, 0.05 mmol), and potassium carbonate (0.07 g, 0.51 mmol)in dioxanes (2 mL) was heated to 200° C. for 20 min in a microwavereactor. Upon cooling to room temperature, an aliquot was analyzed byliquid chromatography/mass spectrometry (LCMS) and found to contain thedesired product. A second portion ofN-[1-(6-chloro-3-pyridinyl)ethyl]-N-cyclopropyl-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide(0.12 g, 0.33 mmol) was reacted as described above, and the two crudereaction mixtures were combined and concentrated under reduced pressure.The residue was chromatographed on silica gel eluting with 80 to 100%ethyl acetate in hexanes to provide the title compound (0.23 g), acompound of the invention, as a brown oil.

¹H NMR δ 8.61 (m, 1H), 8.43 (m, 1H), 8.00 (m, 1H), 7.85 (m, 1H), 7.64(s, 1H), 7.03 (t, 1H), 7.72 (m, 1H), 5.79 (m, 1H), 3.96 (s, 3H), 2.63(m, 1H), 1.83 (d, 3H), 0.65 (m, 2H), 0.55 (m, 1H), 0.35 (m, 1H).

Example 2 Preparation ofN-cyclopropyl-3-(difluoromethyl)-1-methyl-N-[[3-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl]methyl]-1H-pyrazole-4-carboxamide(Compound 9) Step A: Preparation of3-[3-(trifluoromethyl)-1H-pyrazol-1-yl]benzaldehyde

3-Bromobenzaldehyde (1.0 g, 5.4 mmol, 1.0 eq.),3-(trifluoromethyl)-pyrazole (730 mg, 1.0 eq.), Cu(I) iodide (210 mg,0.20 eq.), and cesium carbonate (3.5 g, 2.0 eq.) were placed in areaction vial. The vial was purged with nitrogen andN,N-dimethylformamide (10 mL) was added. The reaction was heated at 120°C. overnight and then cooled to ambient temperature. The resultingsolids were removed by filtration and washed with diethyl ether. Waterwas added to the filtrate, the layers were separated and the aqueousphase was extracted twice with diethyl ether. The combined organicextracts were washed with water (4×), brine, dried (MgSO₄) andconcentrated under reduced pressure. The resulting residue was purifiedby medium pressure liquid chromatography on silica gel eluting with 10to 40% ethyl acetate in hexanes to yield the title compound (200 mg) asa white solid.

¹H NMR δ 10.10 (s, 1H), 8.19-8.24 (m, 1H), 8.03-8.09 (m, 2H), 7.89 (dt,1H), 7.69 (t, 1H), 6.78 (d, 1H).

Step B: Preparation ofN-cyclopropyl-3-[3-(trifluoromethyl)-1H-pyrazol-1-yl]benzenemethanamine

To a solution of 3-[3-(trifluoromethyl)-1H-pyrazol-1-yl]benzaldehyde(i.e. the product of Step A, 200 mg) in methanol (5 mL) was addedcyclopropylamine (1 mL), and the resulting mixture was stirred atambient temperature for 1 h. Excess sodium borohydride was then added,and the reaction mixture was stirred at room temperature for 1 h. Thereaction was quenched by the addition of water. The layers wereseparated and the aqueous layer was extracted with dichloromethane (4×).The combined organic layers were dried (MgSO₄) and concentrated underreduced pressure. The resulting residue was purified by medium pressureliquid chromatography on silica gel eluting with 10 to 60% ethyl acetatein hexanes to yield the title compound (100 mg).

¹H NMR δ 7.95 (dd, 1H), 7.69 (t, 1H), 7.54-7.59 (m, 1H), 7.43 (t, 1H),7.32 (d, 1H), 6.71 (d, 1H), 3.92 (s, 2H), 2.10-2.25 (m, 1H), 0.42-0.48(m, 2H), 0.38-0.42 (m, 2H).

Step C: Preparation ofN-cyclopropyl-3-(difluoromethyl)-1-methyl-N-[[3-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl]methyl]-1H-pyrazole-4-carboxamide

3-(Difluoromethyl)-1-methyl-1H-pyrazole-4-carboxylic acid (30 mg, 0.17mmol, 1 eq.) was dissolved in thionyl chloride (1 mL) and the resultingsolution was heated to reflux for 3 h. The reaction mixture was allowedto cool to room temperature and then concentrated under reducedpressure. To this material was added a solution ofN-cyclopropyl-3-[3-(trifluoromethyl)-1H-pyrazol-1-yl]benzenemethanamine(i.e. the product of Step B, 46 mg, 1.0 eq.) and triethylamine (3.5 eq.)in dichloromethane (4 mL). The reaction mixture was stirred overnight atamient temperature. The reaction was then quenched with water andextracted with dichloromethane. The organic phase was dried (MgSO₄) andconcentrated under reduced pressure. The resulting residue was purifiedby medium pressure liquid chromatography on silica gel eluting with 20to 80% ethyl acetate in hexanes followed by a second purification bymedium pressure liquid chromatography on silica gel eluting with 1 to10% acetone in chloroform to yield the title compound (35 mg), acompound of the invention, as a colorless oil.

¹H NMR δ 7.95 (dd, 1H), 7.67 (d, 2H), 7.62 (dd, 1H), 7.43-7.47 (m, 1H),7.28-7.33 (m, 1H), 6.92-7.20 (m, 1H), 6.72 (d, 1H), 4.80 (s, 2H), 3.96(s, 3H), 2.69-2.79 (m, 1H), 0.67-0.80 (m, 4H).

Example 3 Preparation ofN-[[2-chloro-4-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl]methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide(Compound 12) Step A: Preparation of2-chloro-4-[3-(trifluoromethyl)-1H-pyrazol-1-yl]benzaldehyde

A mixture of 2-chloro-4-fluorobenzaldehyde (7.0 g, 44.3 mmol),3-(trifluoromethyl)-1H-pyrazole (9.03 g, 66.45 mmol) and potassiumcarbonate (12.2 g, 88.6 mmol) in anhydrous N,N-dimethylformamide (70 mL)was stirred for 2 h at 110° C. The reaction mixture was cooled to 0° C.,poured into ice water (800 mL) and stirred for 15 min. The precipitateformed was filtered and dried under reduced pressure to afford the titlecompound (10.2 g), which was used without further purification.

¹H NMR δ 10.4 (s, 1H), 8.00 (m, 2H), 7.85 (d, 1H), 7.77 (m, 1H), 6.70(d, 1H).

Step B: Preparation of2-chloro-N-cyclopropyl-4-[3-(trifluoromethyl)-1H-pyrazol-1-yl]benzenemethanamine

To a solution of2-chloro-4-[3-(trifluoromethyl)-1H-pyrazol-1-yl]benzaldehyde (i.e. theproduct of Step A, 1.0 g, 3.6 mmol) in anhydrous tetrahydrofuran (10 mL)was added cyclopropylamine (0.2 g, 4 mmol) and titanium(IV) isopropoxide(5.2 g, 18.2 mmol) at 0° C. The resulting solution was stirred atambient temperature for 4 h. Sodium borohydride (0.34 g, 9.0 mmol) wasthen added, and the mixture was stirred at room temperature for 6 h. Thereaction mixture was poured into ice water and extracted with ethylacetate (20 mL). The aqueous layer was extracted with ethyl acetate(2×25 mL), and the combined organic layers were washed with brine (50mL), dried (Na₂SO₄) and concentrated under reduced pressure. The residuewas purified by column chromatography on silica gel eluting with 50%ethyl acetate in hexanes to afford the title compound (0.6 g).

Step C: PreparationN4-[[2-chloro-4-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl]methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide

To a solution of2-chloro-N-cyclopropyl-4-[3-(trifluoromethyl)-1H-pyrazol-1-yl]benzenemethanamine(i.e. the product of Step B, 150 mg, 0.47 mmol),N-(3-dimethylaminopropyl)-N-ethylcarbodiimide (137 mg, 0.71 mmol),1-hydroxybenzotriazole (77 mg, 0.57 mmol) and N,N-diisopropylethylamine(0.25 mL, 1.43 mmol) in dichloromethane (5 mL) was added3-difluoromethyl-5-fluoro-1-methyl-1H-pyrazole-4-carboxylic acid (92 mg,0.47 mmol; prepared as described in PCT Patent Publication WO2010/130767), was stirred for 12 h. The reaction mixture was washed withwater, brine, dried (Na₂SO₄) and concentrated under reduced pressure.The residue was purified by column chromatography on silica gel elutingwith 50% ethyl acetate in hexanes to afford the title compound (100 mg),a compound of the invention, as an off-white solid.

¹H NMR δ 7.94 (s, 1H), 7.82 (d, 1H), 7.58 (dd, 1H), 7.40 (d, 1H), 6.80(t, 1H), 6.70 (d, 1H), 4.84 (s, 2H), 3.80 (s, 3H), 2.78 (m, 1H), 0.70(m, 4H).

By the procedures described herein together with methods known in theart, the following compounds of Tables 1 to 1539 can be prepared. Thefollowing abbreviations are used in the Tables which follow: Me meansmethyl, Et means ethyl, Pr means propyl, i-Pr means isopropyl, c-Prmeans cyclopropyl, OMe means methoxy, TMS means trimethylsilyl, Ph meansphenyl, MeOC(═O) means methoxycarbonyl and CN means cyano. “(R³)_(n) isH” means that n is 0 and the ring comprising G is not substituted withR³. The structures of individual “A” substituents in the Tables aredepicted in Exhibit 4.

TABLE 1

A is A-1a and (R³)_(n) is H. Q 3-CF₃-1H-pyrazol-1-yl3-Br-1H-pyrazol-1-yl 4-F-1H-pyrazol-1-yl 5-Me-1H-pyrazol-1-yl3-CHF₂-1H-pyrazol-1-yl 3-I-1H-pyrazol-1-yl 4-Cl-1H-pyrazol-1-yl5-Et-1H-pyrazol-1-yl 3-OMe-1H-pyrazol-1-yl 3-OCHF₂-1H-pyrazol-1-yl4-OCF₃-1H-pyrazol-1-yl 5-CN-1H-pyrazol-1-yl 3-MeOC(═O)-1H-pyrazol-1-yl3,5-di-F-1H-pyrazol-1-yl 3,5-di-CF₃-1H-pyrazol-1-yl 5-Ph-1H-pyrazol-1-yl3-CF₃-5-Me-1H-pyrazol-1-yl 3,4-di-Br-1H-pyrazol-1-yl3-Me-1H-[1,2,4]triazol-1-yl 3-F-1H-[1,2,4]triazol-1-yl3,5-di-Cl-1H-[1,2,4]triazol-1-yl 1H-[1,2,4]triazol-1-yl4-CHF₂-2H-[1,2,3]triazol-2-yl 4-Br-2H-[1,2,3]triazol-2-yl4,5-di-CF₃-2H-[1,2,3]triazol-2-yl 2H-[1,2,3]triazol-2-yl4-CHF₂-1H-[1,2,3]triazol-1-yl 4-Br-1H-[1,2,3]triazol-1-yl3-Me-1H-pyrrol-1-yl 3,4-di-Me-1H-pyrrol-1-yl 2,4-di-CF₃-1H-pyrrol-1-yl1H-pyrrol-1-yl 1-Et-1H-pyrazol-3-yl 1-Ph-1H-pyrazol-3-yl1-Me-1H-pyrazol-4-yl 1-i-Pr-1H-pyrazol-4-yl 1,3-di-Me-1H-pyrazol-4-yl1-Me-1H-[1,2,4]triazol-3-yl 1-i-Pr-1H-[1,2,4]triazol-3-yl3,5-di-Me-1H-[1,2,4]triazol-1-yl 5-CF₃-2,4-dihydro-3-oxopyrazol-1-yl3-Me-1H-pyrazol-1-yl 4-CF₃-1H-pyrazol-1-yl 4-Br-1H-pyrazol-1-yl5-F-1H-pyrazol-1-yl 3-Et-1H-pyrazol-1-yl 4-CHF₂-1H-pyrazol-1-yl4-I-1H-pyrazol-1-yl 5-Cl-1H-pyrazol-1-yl 3-CN-1H-pyrazol-1-yl4-OMe-1H-pyrazol-1-yl 4-OCHF₂-1H-pyrazol-1-yl 5-OCF₃-1H-pyrazol-1-yl3-Ph-1H-pyrazol-1-yl 4-MeOC(═O)-1H-pyrazol-1-yl3,5-di-Cl-1H-pyrazol-1-yl 3,5-di-CHF₂-1H-pyrazol-1-yl3,4-di-Me-1H-pyrazol-1-yl 3,4-di-Cl-1H-pyrazol-1-yl3-CF₃-1H-[1,2,4]triazol-1-yl 3-Cl-1H-[1,2,4]triazol-1-yl3,5-di-Br-1H-[1,2,4]triazol-1-yl 4-Me-2H-[1,2,3]triazol-2-yl4-F-2H-[1,2,3]triazol-2-yl 4-Ph-2H-[1,2,3]triazol-2-yl4,5-di-Cl-2H-[1,2,3]triazol-2-yl 4-Me-1H-[1,2,3]triazol-1-yl4-F-1H-[1,2,3]triazol-1-yl 4-Ph-1H-[1,2,3]triazol-1-yl3-CF₃-1H-pyrrol-1-yl 2,4-di-Me-1H-pyrrol-1-yl 3,4-di-Br-1H-pyrrol-1-yl1-Me-1H-pyrazol-3-yl 1-i-Pr-1H-pyrazol-3-yl 1,4-di-Me-1H-pyrazol-3-yl1-CF₃-1H-pyrazol-4-yl 1-(F₃CCH₂)-1H-pyrazol-4-yl1-Me-3-CF3-1H-pyrazol-4-yl 1-CF₃-1H-[1,2,4]triazol-3-yl1-Ph-1H-[1,2,4]triazol-3-yl 3,5-di-CF₃-1H-[1,2,4]triazol-1-yl5-Me-2,4-dihydro-3-oxopyrazol-1-yl 3-F-1H-pyrazol-1-yl4-Me-1H-pyrazol-1-yl 5-CF₃-1H-pyrazol-1-yl 5-Br-1H-pyrazol-1-yl3-Cl-1H-pyrazol-1-yl 4-Et-1H-pyrazol-1-yl 5-CHF₂-1H-pyrazol-1-yl3-I-1H-pyrazol-1-yl 3-OCF₃-1H-pyrazol-1-yl 4-CN-1H-pyrazol-1-yl5-OCF₃-1H-pyrazol-1-yl 5-OCHF₂-1H-pyrazol-1-yl 3,5-di-Me-1H-pyrazol-1-yl4-Ph-1H-pyrazol-1-yl 5-MeOC(═O)-1H-pyrazol-1-yl3,5-di-Br-1H-pyrazol-1-yl 3,4-di-CF₃-1H-pyrazol-1-yl 1H-pyrazol-1-yl3-CHF₂-1H-[1,2,4]triazol-1-yl 3-Br-1H-[1,2,4]triazol-1-yl3-Ph-1H-[1,2,4]triazol-1-yl 4-CF₃-2H-[1,2,3]triazol-2-yl4-Cl-2H-[1,2,3]triazol-2-yl 4,5-di-Me-2H-[1,2,3]triazol-2-yl4,5-di-Br-2H-[1,2,3]triazol-2-yl 4-CF₃-1H-[1,2,3]triazol-1-yl4-Cl-1H-[1,2,3]triazol-1-yl 1H-[1,2,3]triazol-1-yl 3-CHF₂-1H-pyrrol-1-yl3,4-di-CF₃-1H-pyrrol-1-yl 3,4-di-Cl-1H-pyrrol-1-yl 1-CF₃-1H-pyrazol-3-yl1-(F₃CCH₂)-1H-pyrazol-3-yl 1-Me-4-CF₃-1H-pyrazol-3-yl1-Et-1H-pyrazol-4-yl 1-Ph-1H-pyrazol-4-yl 3-Me-1-CF₃-1H-pyrazol-4-yl1-Et-1H-[1,2,4]triazol-3-yl 5-Ph-4,5-dihydro-isoxazol-3-yl3,5-di-CHF₂-1H-[1,2,4]triazol-1-yl

The present disclosure also includes Tables 2 through 769, each of whichis constructed the same as Table 1 above, except that the row heading inTable 1 (i.e. “A is A-1a and R³ is H.”) is replaced with the respectiverow heading shown below. For example, in Table 2 the row heading is “Ais A-1a and R³ is 2-F and Q is as defined in Table 1 above. Thus, thefirst entry in Table 2 specifically disclosesN-[[2-fluoro-4-(3-trifluoromethyl-1H-pyrazol-1-yl)phenyl]methyl]-N-cyclopropyl-3-(trifluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.Tables 3 through 769 are constructed similarly.

TABLES 2-761 Table Row Heading 2 A is A-1a and (R³)_(n) is 2-F. 3 A isA-1a and (R³)_(n) is 2,3-di-F. 4 A is A-1a and (R³)_(n) is 2,6-di-F. 5 Ais A-1a and (R³)_(n) is 2-Cl. 6 A is A-1a and (R³)_(n) is 2,3-di-Cl. 7 Ais A-1a and (R³)_(n) is 2,6-di-Cl. 8 A is A-1a and (R³)_(n) is 2-Br. 9 Ais A-1a and (R³)_(n) is 2,3-di-Br. 10 A is A-1a and (R³)_(n) is2,6-di-Br. 11 A is A-1a and (R³)_(n) is 2-I. 12 A is A-1a and (R³)_(n)is 2,3-di-I. 13 A is A-1a and (R³)_(n) is 2,6-di-I. 14 A is A-1a and(R³)_(n) is 2-Me. 15 A is A-1a and (R³)_(n) is 2,3-di-Me. 16 A is A-1aand (R³)_(n) is 2,6-di-Me. 17 A is A-1a and (R³)_(n) is 2-Et. 18 A isA-1a and (R³)_(n) is 2,3-di-Et. 19 A is A-1a and (R³)_(n) is 2,6-di-Et.20 A is A-1a and (R³)_(n) is 2-i-Pr. 21 A is A-1a and (R³)_(n) is2,3-di-i-Pr. 22 A is A-1a and (R³)_(n) is 2,6-di-i-Pr. 23 A is A-1a and(R³)_(n) is 2-c-Pr. 24 A is A-1a and (R³)_(n) is 2,3-di-c-Pr. 25 A isA-1a and (R³)_(n) is 2,6-di-c-Pr. 26 A is A-1a and (R³)_(n) is 2-CF3. 27A is A-1a and (R³)_(n) is 2,3-di-CF₃. 28 A is A-1a and (R³)_(n) is2,6-di-CF₃. 29 A is A-1a and (R³)_(n) is 2-OMe. 30 A is A-1a and(R³)_(n) is 2,3-di-OMe. 31 A is A-1a and (R³)_(n) is 2,6-di-OMe. 32 A isA-1a and (R³)_(n) is 2-OCF₃. 33 A is A-1a and (R³)_(n) is 2,3-di-OCF₃.34 A is A-1a and (R³)_(n) is 2,6-di-OCF₃. 35 A is A-1a and (R³)_(n) is2-TMS. 36 A is A-1a and (R³)_(n) is 2,3-di-TMS. 37 A is A-1a and(R³)_(n) is 2,6-di-TMS. 38 A is A-1a and (R³)_(n) is 2-Cl-6-F. 39 A isA-1a and (R³)_(n) is 2-Cl-5-F. 40 A is A-1b and (R³)_(n) is H. 41 A isA-1b and (R³)_(n) is 2-F. 42 A is A-1b and (R³)_(n) is 2,3-di-F. 43 A isA-1b and (R³)_(n) is 2,6-di-F. 44 A is A-1b and (R³)_(n) is 2-Cl. 45 Ais A-1b and (R³)_(n) is 2,3-di-Cl. 46 A is A-1b and (R³)_(n) is2,6-di-Cl. 47 A is A-1b and (R³)_(n) is 2-Br. 48 A is A-1b and (R³)_(n)is 2,3-di-Br. 49 A is A-1b and (R³)_(n) is 2,6-di-Br. 50 A is A-1b and(R³)_(n) is 2-I. 51 A is A-1b and (R³)_(n) is 2,3-di-I. 52 A is A-1b and(R³)_(n) is 2,6-di-I. 53 A is A-1b and (R³)_(n) is 2-Me. 54 A is A-1band (R³)_(n) is 2,3-di-Me. 55 A is A-1b and (R³)_(n) is 2,6-di-Me. 56 Ais A-1b and (R³)_(n) is 2-Et. 57 A is A-1b and (R³)_(n) is 2,3-di-Et. 58A is A-1b and (R³)_(n) is 2,6-di-Et. 59 A is A-1b and (R³)_(n) is2-i-Pr. 60 A is A-1b and (R³)_(n) is 2,3-di-i-Pr. 61 A is A-1b and(R³)_(n) is 2,6-di-i-Pr. 62 A is A-1b and (R³)_(n) is 2-c-Pr. 63 A isA-1b and (R³)_(n) is 2,3-di-c-Pr. 64 A is A-1b and (R³)_(n) is2,6-di-c-Pr. 65 A is A-1b and (R³)_(n) is 2-CF₃. 66 A is A-1b and(R³)_(n) is 2,3-di-CF₃. 67 A is A-1b and (R³)_(n) is 2,6-di-CF₃. 68 A isA-1b and (R³)_(n) is 2-OMe. 69 A is A-1b and (R³)_(n) is 2,3-di-OMe. 70A is A-1b and (R³)_(n) is 2,6-di-OMe. 71 A is A-1b and (R³)_(n) is2-OCF₃. 72 A is A-1b and (R³)_(n) is 2,3-di-OCF₃. 73 A is A-1b and(R³)_(n) is 2,6-di-OCF₃. 74 A is A-1b and (R³)_(n) is 2-TMS. 75 A isA-1b and (R³)_(n) is 2,3-di-TMS. 76 A is A-1b and (R³)_(n) is2,6-di-TMS. 77 A is A-1b and (R³)_(n) is 2-Cl-6-F. 78 A is A-1b and(R³)_(n) is 2-Cl-5-F. 78 A is A-1c and (R³)_(n) is H. 79 A is A-1c and(R³)_(n) is 2-F. 80 A is A-1c and (R³)_(n) is 2,3-di-F. 81 A is A-1c and(R³)_(n) is 2,6-di-F. 82 A is A-1c and (R³)_(n) is 2-Cl. 83 A is A-1cand (R³)_(n) is 2,3-di-Cl. 84 A is A-1c and (R³)_(n) is 2,6-di-Cl. 85 Ais A-1c and (R³)_(n) is 2-Br. 86 A is A-1c and (R³)_(n) is 2,3-di-Br. 87A is A-1c and (R³)_(n) is 2,6-di-Br. 88 A is A-1c and (R³)_(n) is 2-I.89 A is A-1c and (R³)_(n) is 2,3-di-I. 90 A is A-1c and (R³)_(n) is2,6-di-I. 91 A is A-1c and (R³)_(n) is 2-Me. 92 A is A-1c and (R³)_(n)is 2,3-di-Me. 93 A is A-1c and (R³)_(n) is 2,6-di-Me. 94 A is A-1c and(R³)_(n) is 2-Et. 95 A is A-1c and (R³)_(n) is 2,3-di-Et. 96 A is A-1cand (R³)_(n) is 2,6-di-Et. 97 A is A-1c and (R³)_(n) is 2-i-Pr. 98 A isA-1c and (R³)_(n) is 2,3-di-i-Pr. 99 A is A-1c and (R³)_(n) is2,6-di-i-Pr. 100 A is A-1c and (R³)_(n) is 2-c-Pr. 101 A is A-1c and(R³)_(n) is 2,3-di-c-Pr. 102 A is A-1c and (R³)_(n) is 2,6-di-c-Pr. 103A is A-1c and (R³)_(n) is 2-CF₃. 104 A is A-1c and (R³)_(n) is2,3-di-CF₃. 105 A is A-1c and (R³)_(n) is 2,6-di-CF₃. 106 A is A-1c and(R³)_(n) is 2-OMe. 107 A is A-1c and (R³)_(n) is 2,3-di-OMe. 108 A isA-1c and (R³)_(n) is 2,6-di-OMe. 109 A is A-1c and (R³)_(n) is 2-OCF₃.110 A is A-1c and (R³)_(n) is 2,3-di-OCF₃. 111 A is A-1c and (R³)_(n) is2,6-di-OCF₃. 112 A is A-1c and (R³)_(n) is 2-TMS. 113 A is A-1c and(R³)_(n) is 2,3-di-TMS. 114 A is A-1c and (R³)_(n) is 2,6-di-TMS. 115 Ais A-1c and (R³)_(n) is 2-Cl-6-F. 116 A is A-1c and (R³)_(n) is2-Cl-5-F. 117 A is A-1d and (R³)_(n) is H. 118 A is A-1d and (R³)_(n) is2-F. 119 A is A-1d and (R³)_(n) is 2,3-di-F. 120 A is A-1d and (R³)_(n)is 2,6-di-F. 121 A is A-1d and (R³)_(n) is 2-Cl. 122 A is A-1d and(R³)_(n) is 2,3-di-Cl. 123 A is A-1d and (R³)_(n) is 2,6-di-Cl. 124 A isA-1d and (R³)_(n) is 2-Br. 125 A is A-1d and (R³)_(n) is 2,3-di-Br. 126A is A-1d and (R³)_(n) is 2,6-di-Br. 127 A is A-1d and (R³)_(n) is 2-I.128 A is A-1d and (R³)_(n) is 2,3-di-I. 129 A is A-1d and (R³)_(n) is2,6-di-I. 130 A is A-1d and (R³)_(n) is 2-Me. 131 A is A-1d and (R³)_(n)is 2,3-di-Me. 132 A is A-1d and (R³)_(n) is 2,6-di-Me. 133 A is A-1d and(R³)_(n) is 2-Et. 134 A is A-1d and (R³)_(n) is 2,3-di-Et. 135 A is A-1dand (R³)_(n) is 2,6-di-Et. 136 A is A-1d and (R³)_(n) is 2-i-Pr. 137 Ais A-1d and (R³)_(n) is 2,3-di-i-Pr. 138 A is A-1d and (R³)_(n) is2,6-di-i-Pr. 139 A is A-1d and (R³)_(n) is 2-c-Pr. 140 A is A-1d and(R³)_(n) is 2,3-di-c-Pr. 141 A is A-1d and (R³)_(n) is 2,6-di-c-Pr. 142A is A-1d and (R³)_(n) is 2-CF₃. 143 A is A-1d and (R³)_(n) is2,3-di-CF₃. 144 A is A-1d and (R³)_(n) is 2,6-di-CF₃. 145 A is A-1d and(R³)_(n) is 2-OMe. 146 A is A-1d and (R³)_(n) is 2,3-di-OMe. 147 A isA-1d and (R³)_(n) is 2,6-di-OMe. 148 A is A-1d and (R³)_(n) is 2-OCF₃.149 A is A-1d and (R³)_(n) is 2,3-di-OCF₃. 150 A is A-1d and (R³)_(n) is2,6-di-OCF₃. 151 A is A-1d and (R³)_(n) is 2-TMS. 152 A is A-1d and(R³)_(n) is 2,3-di-TMS. 153 A is A-1d and (R³)_(n) is 2,6-di-TMS. 154 Ais A-1d and (R³)_(n) is 2-Cl-6-F. 155 A is A-1d and (R³)_(n) is2-Cl-5-F. 156 A is A-1e and (R³)_(n) is H. 157 A is A-1e and (R³)_(n) is2-F. 158 A is A-1e and (R³)_(n) is 2,3-di-F. 159 A is A-1e and (R³)_(n)is 2,6-di-F. 160 A is A-1e and (R³)_(n) is 2-Cl. 161 A is A-1e and(R³)_(n) is 2,3-di-Cl. 162 A is A-1e and (R³)_(n) is 2,6-di-Cl. 163 A isA-1e and (R³)_(n) is 2-Br. 164 A is A-1e and (R³)_(n) is 2,3-di-Br. 165A is A-1e and (R³)_(n) is 2,6-di-Br. 166 A is A-1e and (R³)_(n) is 2-I.167 A is A-1e and (R³)_(n) is 2,3-di-I. 168 A is A-1e and (R³)_(n) is2,6-di-I. 169 A is A-1e and (R³)_(n) is 2-Me. 170 A is A-1e and (R³)_(n)is 2,3-di-Me. 171 A is A-1e and (R³)_(n) is 2,6-di-Me. 172 A is A-1e and(R³)_(n) is 2-Et. 173 A is A-1e and (R³)_(n) is 2,3-di-Et. 174 A is A-1eand (R³)_(n) is 2,6-di-Et. 175 A is A-1e and (R³)_(n) is 2-i-Pr. 176 Ais A-1e and (R³)_(n) is 2,3-di-i-Pr. 177 A is A-1e and (R³)_(n) is2,6-di-i-Pr. 178 A is A-1e and (R³)_(n) is 2-c-Pr. 179 A is A-1e and(R³)_(n) is 2,3-di-c-Pr. 180 A is A-1e and (R³)_(n) is 2,6-di-c-Pr. 181A is A-1e and (R³)_(n) is 2-CF₃. 182 A is A-1e and (R³)_(n) is2,3-di-CF₃. 183 A is A-1e and (R³)_(n) is 2,6-di-CF₃. 184 A is A-1e and(R³)_(n) is 2-OMe. 185 A is A-1e and (R³)_(n) is 2,3-di-OMe. 186 A isA-1e and (R³)_(n) is 2,6-di-OMe. 187 A is A-1e and (R³)_(n) is 2-OCF₃.188 A is A-1e and (R³)_(n) is 2,3-di-OCF₃. 189 A is A-1e and (R³)_(n) is2,6-di-OCF₃. 190 A is A-1e and (R³)_(n) is 2-TMS. 191 A is A-1e and(R³)_(n) is 2,3-di-TMS. 192 A is A-1e and (R³)_(n) is 2,6-di-TMS. 193 Ais A-1e and (R³)_(n) is 2-Cl-6-F. 194 A is A-1e and (R³)_(n) is2-Cl-5-F. 195 A is A-1f and (R³)_(n) is H. 196 A is A-1f and (R³)_(n) is2-F. 197 A is A-1f and (R³)_(n) is 2,3-di-F. 198 A is A-1f and (R³)_(n)is 2,6-di-F. 199 A is A-1f and (R³)_(n) is 2-Cl. 200 A is A-1f and(R³)_(n) is 2,3-di-Cl. 201 A is A-1f and (R³)_(n) is 2,6-di-Cl. 202 A isA-1f and (R³)_(n) is 2-Br. 203 A is A-1f and (R³)_(n) is 2,3-di-Br. 204A is A-1f and (R³)_(n) is 2,6-di-Br. 205 A is A-1f and (R³)_(n) is 2-I.206 A is A-1f and (R³)_(n) is 2,3-di-I. 207 A is A-1f and (R³)_(n) is2,6-di-I. 208 A is A-1f and (R³)_(n) is 2-Me. 209 A is A-1f and (R³)_(n)is 2,3-di-Me. 210 A is A-1f and (R³)_(n) is 2,6-di-Me. 211 A is A-1f and(R³)_(n) is 3-Et. 212 A is A-1f and (R³)_(n) is 2,5-di-Et. 213 A is A-1fand (R³)_(n) is 3,5-di-Et. 214 A is A-1f and (R³)_(n) is 3-i-Pr. 215 Ais A-1f and (R³)_(n) is 2,5-di-i-Pr. 216 A is A-1f and (R³)_(n) is3,5-di-i-Pr. 217 A is A-1f and (R³)_(n) is 3-c-Pr. 218 A is A-1f and(R³)_(n) is 2,5-di-c-Pr. 219 A is A-1f and (R³)_(n) is 3,5-di-c-Pr. 220A is A-1f and (R³)_(n) is 3-CF₃. 221 A is A-1f and (R³)_(n) is2,5-di-CF₃. 222 A is A-1f and (R³)_(n) is 3,5-di-CF₃. 223 A is A-1f and(R³)_(n) is 3-OMe. 224 A is A-1f and (R³)_(n) is 2,5-di-OMe. 225 A isA-1f and (R³)_(n) is 3,5-di-OMe. 226 A is A-1f and (R³)_(n) is 3-OCF₃.227 A is A-1f and (R³)_(n) is 2,5-di-OCF₃. 228 A is A-1f and (R³)_(n) is3,5-di-OCF₃. 229 A is A-1f and (R³)_(n) is 3-TMS. 230 A is A-1f and(R³)_(n) is 2,5-di-TMS. 231 A is A-1f and (R³)_(n) is 3,5-di-TMS. 232 Ais A-1f and (R³)_(n) is 2-Cl-6-Me. 233 A is A-1f and (R³)_(n) is2-Cl-5-Me. 234 A is A-1g and (R³)_(n) is H. 235 A is A-1g and (R³)_(n)is 3-F. 236 A is A-1g and (R³)_(n) is 2,5-di-F. 237 A is A-1g and(R³)_(n) is 3,5-di-F. 238 A is A-1g and (R³)_(n) is 3-Cl. 239 A is A-1gand (R³)_(n) is 2,5-di-Cl. 240 A is A-1g and (R³)_(n) is 3,5-di-Cl. 241A is A-1g and (R³)_(n) is 3-Br. 242 A is A-1g and (R³)_(n) is 2,5-di-Br.243 A is A-1g and (R³)_(n) is 3,5-di-Br. 244 A is A-1g and (R³)_(n) is3-I. 245 A is A-1g and (R³)_(n) is 2,5-di-I. 246 A is A-1g and (R³)_(n)is 3,5-di-I. 247 A is A-1g and (R³)_(n) is 3-Me. 248 A is A-1g and(R³)_(n) is 2,5-di-Me. 249 A is A-1g and (R³)_(n) is 3,5-di-Me. 250 A isA-1g and (R³)_(n) is 3-Et. 251 A is A-1g and (R³)_(n) is 2,5-di-Et. 252A is A-1g and (R³)_(n) is 3,5-di-Et. 253 A is A-1g and (R³)_(n) is3-i-Pr. 254 A is A-1g and (R³)_(n) is 2,5-di-i-Pr. 255 A is A-1g and(R³)_(n) is 3,5-di-i-Pr. 256 A is A-1g and (R³)_(n) is 3-c-Pr. 257 A isA-1g and (R³)_(n) is 2,5-di-c-Pr. 258 A is A-1g and (R³)_(n) is3,5-di-c-Pr. 259 A is A-1g and (R³)_(n) is 3-CF₃. 260 A is A-1g and(R³)_(n) is 2,5-di-CF₃. 261 A is A-1g and (R³)_(n) is 3,5-di-CF₃. 262 Ais A-1g and (R³)_(n) is 3-OMe. 263 A is A-1g and (R³)_(n) is 2,5-di-OMe.264 A is A-1g and (R³)_(n) is 3,5-di-OMe. 265 A is A-1g and (R³)_(n) is3-OCF₃. 266 A is A-1g and (R³)_(n) is 2,5-di-OCF₃. 267 A is A-1g and(R³)_(n) is 3,5-di-OCF₃. 268 A is A-1g and (R³)_(n) is 3-TMS. 269 A isA-1g and (R³)_(n) is 2,5-di-TMS. 270 A is A-1g and (R³)_(n) is3,5-di-TMS. 271 A is A-1g and (R³)_(n) is 2-Cl-6-Me. 272 A is A-1g and(R³)_(n) is 2-Cl-5-Me. 273 A is A-1h and (R³)_(n) is H. 274 A is A-1hand (R³)_(n) is 3-F. 275 A is A-1h and (R³)_(n) is 2,5-di-F. 276 A isA-1h and (R³)_(n) is 3,5-di-F. 277 A is A-1h and (R³)_(n) is 3-Cl. 278 Ais A-1h and (R³)_(n) is 2,5-di-Cl. 279 A is A-1h and (R³)_(n) is3,5-di-Cl. 280 A is A-1h and (R³)_(n) is 3-Br. 281 A is A-1h and(R³)_(n) is 2,5-di-Br. 282 A is A-1h and (R³)_(n) is 3,5-di-Br. 283 A isA-1h and (R³)_(n) is 3-I. 284 A is A-1h and (R³)_(n) is 2,5-di-I. 285 Ais A-1h and (R³)_(n) is 3,5-di-I. 286 A is A-1h and (R³)_(n) is 3-Me.287 A is A-1h and (R³)_(n) is 2,5-di-Me. 288 A is A-1h and (R³)_(n) is3,5-di-Me. 289 A is A-1h and (R³)_(n) is 3-Et. 290 A is A-1h and(R³)_(n) is 2,5-di-Et. 291 A is A-1h and (R³)_(n) is 3,5-di-Et. 292 A isA-1h and (R³)_(n) is 3-i-Pr. 293 A is A-1h and (R³)_(n) is 2,5-di-i-Pr.294 A is A-1h and (R³)_(n) is 3,5-di-i-Pr. 295 A is A-1h and (R³)_(n) is3-c-Pr. 296 A is A-1h and (R³)_(n) is 2,5-di-c-Pr. 297 A is A-1h and(R³)_(n) is 3,5-di-c-Pr. 298 A is A-1h and (R³)_(n) is 3-CF₃. 299 A isA-1h and (R³)_(n) is 2,5-di-CF₃. 300 A is A-1h and (R³)_(n) is3,5-di-CF₃. 301 A is A-1h and (R³)_(n) is 3-OMe. 302 A is A-1h and(R³)_(n) is 2,5-di-OMe. 303 A is A-1h and (R³)_(n) is 3,5-di-OMe. 304 Ais A-1h and (R³)_(n) is 3-OCF₃. 305 A is A-1h and (R³)_(n) is2,5-di-OCF₃. 306 A is A-1h and (R³)_(n) is 3,5-di-OCF₃. 307 A is A-1hand (R³)_(n) is 3-TMS. 308 A is A-1h and (R³)_(n) is 2,5-di-TMS. 309 Ais A-1h and (R³)_(n) is 3,5-di-TMS. 310 A is A-1h and (R³)_(n) is2-Cl-6-Me. 311 A is A-1h and (R³)_(n) is 2-Cl-5-Me. 312 A is A-1i and(R³)_(n) is H. 313 A is A-1i and (R³)_(n) is 3-F. 314 A is A-1i and(R³)_(n) is 2,5-di-F. 315 A is A-1i and (R³)_(n) is 3,5-di-F. 316 A isA-1i and (R³)_(n) is 3-Cl. 317 A is A-1i and (R³)_(n) is 2,5-di-Cl. 318A is A-1i and (R³)_(n) is 3,5-di-Cl. 319 A is A-1i and (R³)_(n) is 3-Br.320 A is A-1i and (R³)_(n) is 2,5-di-Br. 321 A is A-1i and (R³)_(n) is3,5-di-Br. 322 A is A-1i and (R³)_(n) is 3-I. 323 A is A-1i and (R³)_(n)is 2,5-di-I. 324 A is A-1i and (R³)_(n) is 3,5-di-I. 325 A is A-1i and(R³)_(n) is 3-Me. 326 A is A-1i and (R³)_(n) is 2,5-di-Me. 327 A is A-1iand (R³)_(n) is 3,5-di-Me. 328 A is A-1i and (R³)_(n) is 3-Et. 329 A isA-1i and (R³)_(n) is 2,5-di-Et. 330 A is A-1i and (R³)_(n) is 3,5-di-Et.331 A is A-1i and (R³)_(n) is 3-i-Pr. 332 A is A-1i and (R³)_(n) is2,5-di-i-Pr. 333 A is A-1i and (R³)_(n) is 3,5-di-i-Pr. 334 A is A-1iand (R³)_(n) is 3-c-Pr. 335 A is A-1i and (R³)_(n) is 2,5-di-c-Pr. 336 Ais A-1i and (R³)_(n) is 3,5-di-c-Pr. 337 A is A-1i and (R³)_(n) is3-CF₃. 338 A is A-1i and (R³)_(n) is 2,5-di-CF₃. 339 A is A-1i and(R³)_(n) is 3,5-di-CF₃. 340 A is A-1i and (R³)_(n) is 3-OMe. 341 A isA-1i and (R³)_(n) is 2,5-di-OMe. 342 A is A-1i and (R³)_(n) is3,5-di-OMe. 343 A is A-1i and (R³)_(n) is 3-OCF₃. 344 A is A-1i and(R³)_(n) is 2,5-di-OCF₃. 345 A is A-1i and (R³)_(n) is 3,5-di-OCF₃. 346A is A-1i and (R³)_(n) is 3-TMS. 347 A is A-1i and (R³)_(n) is2,5-di-TMS. 348 A is A-1i and (R³)_(n) is 3,5-di-TMS. 349 A is A-1i and(R³)_(n) is 2-Cl-6-Me. 350 A is A-1i and (R³)_(n) is 2-Cl-5-Me. 351 A isA-1j and (R³)_(n) is H. 352 A is A-1j and (R³)_(n) is 3-F. 353 A is A-1jand (R³)_(n) is 2,5-di-F. 354 A is A-1j and (R³)_(n) is 3,5-di-F. 355 Ais A-1j and (R³)_(n) is 3-Cl. 356 A is A-1j and (R³)_(n) is 2,5-di-Cl.357 A is A-1j and (R³)_(n) is 3,5-di-Cl. 358 A is A-1j and (R³)_(n) is3-Br. 359 A is A-1j and (R³)_(n) is 2,5-di-Br. 360 A is A-1j and(R³)_(n) is 3,5-di-Br. 361 A is A-1j and (R³)_(n) is 3-I. 362 A is A-1jand (R³)_(n) is 2,5-di-I. 363 A is A-1j and (R³)_(n) is 3,5-di-I. 364 Ais A-1j and (R³)_(n) is 3-Me. 365 A is A-1j and (R³)_(n) is 2,5-di-Me.366 A is A-1j and (R³)_(n) is 3,5-di-Me. 367 A is A-1j and (R³)_(n) is3-Et. 368 A is A-1j and (R³)_(n) is 2,5-di-Et. 369 A is A-1j and(R³)_(n) is 3,5-di-Et. 370 A is A-1j and (R³)_(n) is 3-i-Pr. 371 A isA-1j and (R³)_(n) is 2,5-di-i-Pr. 372 A is A-1j and (R³)_(n) is3,5-di-i-Pr. 373 A is A-1j and (R³)_(n) is 3-c-Pr. 374 A is A-1j and(R³)_(n) is 2,5-di-c-Pr. 375 A is A-1j and (R³)_(n) is 3,5-di-c-Pr 376 Ais A-1j and (R³)_(n) is 3-CF₃. 377 A is A-1j and (R³)_(n) is 2,5-di-CF₃.378 A is A-1j and (R³)_(n) is 3,5-di-CF₃. 379 A is A-1j and (R³)_(n) is3-OMe. 380 A is A-1j and (R³)_(n) is 2,5-di-OMe. 381 A is A-1j and(R³)_(n) is 3,5-di-OMe. 382 A is A-1j and (R³)_(n) is 3-OCF₃. 383 A isA-1j and (R³)_(n) is 2,5-di-OCF₃. 384 A is A-1j and (R³)_(n) is3,5-di-OCF₃. 385 A is A-1j and (R³)_(n) is 3-TMS. 386 A is A-1j and(R³)_(n) is 2,5-di-TMS. 387 A is A-1j and (R³)_(n) is 3,5-di-TMS. 388 Ais A-1j and (R³)_(n) is 2-Cl-6-Me. 389 A is A-1j and (R³)_(n) is2-Cl-5-Me. 390 A is A-1a and (R³)_(n) is 3-F. 391 A is A-1a and (R³)_(n)is 2,5-di-F. 392 A is A-1a and (R³)_(n) is 3,5-di-F. 393 A is A-1a and(R³)_(n) is 3-Cl. 394 A is A-1a and (R³)_(n) is 2,5-di-Cl. 395 A is A-1aand (R³)_(n) is 3,5-di-Cl. 396 A is A-1a and (R³)_(n) is 3-Br. 397 A isA-1a and (R³)_(n) is 2,5-di-Br. 398 A is A-1a and (R³)_(n) is 3,5-di-Br.399 A is A-1a and (R³)_(n) is 3-I. 400 A is A-1a and (R³)_(n) is2,5-di-I. 401 A is A-1a and (R³)_(n) is 3,5-di-I. 402 A is A-1a and(R³)_(n) is 3-Me. 403 A is A-1a and (R³)_(n) is 2,5-di-Me. 404 A is A-1aand (R³)_(n) is 3,5-di-Me. 405 A is A-1a and (R³)_(n) is 3-Et. 406 A isA-1a and (R³)_(n) is 2,5-di-Et. 407 A is A-1a and (R³)_(n) is 3,5-di-Et.408 A is A-1a and (R³)_(n) is 3-i-Pr. 409 A is A-1a and (R³)_(n) is2,5-di-i-Pr. 410 A is A-1a and (R³)_(n) is 3,5-di-i-Pr. 411 A is A-1aand (R³)_(n) is 3-c-Pr. 412 A is A-1a and (R³)_(n) is 2,5-di-c-Pr. 413 Ais A-1a and (R³)_(n) is 3,5-di-c-Pr. 414 A is A-1a and (R³)_(n) is3-CF₃. 415 A is A-1a and (R³)_(n) is 2,5-di-CF₃. 416 A is A-1a and(R³)_(n) is 3,5-di-CF₃. 417 A is A-1a and (R³)_(n) is 3-OMe. 418 A isA-1a and (R³)_(n) is 2,5-di-OMe. 419 A is A-1a and (R³)_(n) is3,5-di-OMe. 420 A is A-1a and (R³)_(n) is 3-OCF₃. 421 A is A-1a and(R³)_(n) is 2,5-di-OCF₃. 422 A is A-1a and (R³)_(n) is 3,5-di-OCF₃. 423A is A-1a and (R³)_(n) is 3-TMS. 424 A is A-1a and (R³)_(n) is2,5-di-TMS. 425 A is A-1a and (R³)_(n) is 3,5-di-TMS. 426 A is A-1a and(R³)_(n) is 2-Cl-6-Me. 427 A is A-1a and (R³)_(n) is 2-Cl-5-Me. 428 A isA-1b and (R³)_(n) is 3-F. 429 A is A-1b and (R³)_(n) is 2,5-di-F. 430 Ais A-1b and (R³)_(n) is 3,5-di-F. 431 A is A-1b and (R³)_(n) is 3-Cl.432 A is A-1b and (R³)_(n) is 2,5-di-Cl. 433 A is A-1b and (R³)_(n) is3,5-di-Cl. 434 A is A-1b and (R³)_(n) is 3-Br. 435 A is A-1b and(R³)_(n) is 2,5-di-Br. 436 A is A-1b and (R³)_(n) is 3,5-di-Br. 437 A isA-1b and (R³)_(n) is 3-I. 438 A is A-1b and (R³)_(n) is 2,5-di-I. 439 Ais A-1b and (R³)_(n) is 3,5-di-I. 440 A is A-1b and (R³)_(n) is 3-Me.441 A is A-1b and (R³)_(n) is 2,5-di-Me. 442 A is A-1b and (R³)_(n) is3,5-di-Me. 443 A is A-1b and (R³)_(n) is 3-Et. 444 A is A-1b and(R³)_(n) is 2,5-di-Et. 445 A is A-1b and (R³)_(n) is 3,5-di-Et. 446 A isA-1b and (R³)_(n) is 3-i-Pr. 447 A is A-1b and (R³)_(n) is 2,5-di-i-Pr.448 A is A-1b and (R³)_(n) is 3,5-di-i-Pr. 449 A is A-1b and (R³)_(n) is3-c-Pr. 450 A is A-1b and (R³)_(n) is 2,5-di-c-Pr. 451 A is A-1b and(R³)_(n) is 3,5-di-c-Pr. 452 A is A-1b and (R³)_(n) is 3-CF₃. 453 A isA-1b and (R³)_(n) is 2,5-di-CF₃. 454 A is A-1b and (R³)_(n) is3,5-di-CF₃. 455 A is A-1b and (R³)_(n) is 3-OMe. 456 A is A-1b and(R³)_(n) is 2,5-di-OMe. 457 A is A-1b and (R³)_(n) is 3,5-di-OMe. 458 Ais A-1b and (R³)_(n) is 3-OCF₃. 459 A is A-1b and (R³)_(n) is2,5-di-OCF₃ 460 A is A-1b and (R³)_(n) is 3,5-di-OCF₃. 461 A is A-1b and(R³)_(n) is 3-TMS. 462 A is A-1b and (R³)_(n) is 2,5-di-TMS. 463 A isA-1b and (R³)_(n) is 3,5-di-TMS. 464 A is A-1b and (R³)_(n) is2-Cl-6-Me. 465 A is A-1b and (R³)_(n) is 2-Cl-5-Me. 466 A is A-1c and(R³)_(n) is 3-F. 467 A is A-1c and (R³)_(n) is 2,5-di-F. 468 A is A-1cand (R³)_(n) is 3,5-di-F. 469 A is A-1c and (R³)_(n) is 3-Cl. 470 A isA-1c and (R³)_(n) is 2,5-di-Cl. 471 A is A-1c and (R³)_(n) is 3,5-di-Cl.472 A is A-1c and (R³)_(n) is 3-Br. 473 A is A-1c and (R³)_(n) is2,5-di-Br. 474 A is A-1c and (R³)_(n) is 3,5-di-Br. 475 A is A-1c and(R³)_(n) is 3-I. 476 A is A-1c and (R³)_(n) is 2,5-di-I. 477 A is A-1cand (R³)_(n) is 3,5-di-I. 478 A is A-1c and (R³)_(n) is 3-Me. 479 A isA-1c and (R³)_(n) is 2,5-di-Me. 480 A is A-1c and (R³)_(n) is 3,5-di-Me.481 A is A-1c and (R³)_(n) is 3-Et. 482 A is A-1c and (R³)_(n) is2,5-di-Et. 483 A is A-1c and (R³)_(n) is 3,5-di-Et. 484 A is A-1c and(R³)_(n) is 3-i-Pr. 485 A is A-1c and (R³)_(n) is 2,5-di-i-Pr. 486 A isA-1c and (R³)_(n) is 3,5-di-i-Pr. 487 A is A-1c and (R³)_(n) is 3-c-Pr.488 A is A-1c and (R³)_(n) is 2,5-di-c-Pr. 489 A is A-1c and (R³)_(n) is3,5-di-c-Pr. 490 A is A-1c and (R³)_(n) is 3-CF₃. 491 A is A-1c and(R³)_(n) is 2,5-di-CF₃. 492 A is A-1c and (R³)_(n) is 3,5-di-CF₃. 493 Ais A-1c and (R³)_(n) is 3-OMe. 494 A is A-1c and (R³)_(n) is 2,5-di-OMe.495 A is A-1c and (R³)_(n) is 3,5-di-OMe. 496 A is A-1c and (R³)_(n) is3-OCF₃. 497 A is A-1c and (R³)_(n) is 2,5-di-OCF₃. 498 A is A-1c and(R³)_(n) is 3,5-di-OCF₃. 499 A is A-1c and (R³)_(n) is 3-TMS. 500 A isA-1c and (R³)_(n) is 2,5-di-TMS. 501 A is A-1c and (R³)_(n) is3,5-di-TMS. 502 A is A-1c and (R³)_(n) is 2-Cl-6-Me. 503 A is A-1c and(R³)_(n) is 2-Cl-5-Me. 504 A is A-1d and (R³)_(n) is 3-F. 505 A is A-1dand (R³)_(n) is 2,5-di-F. 506 A is A-1d and (R³)_(n) is 3,5-di-F. 507 Ais A-1d and (R³)_(n) is 3-Cl. 508 A is A-1d and (R³)_(n) is 2,5-di-Cl.509 A is A-1d and (R³)_(n) is 3,5-di-Cl. 510 A is A-1d and (R³)_(n) is3-Br. 511 A is A-1d and (R³)_(n) is 2,5-di-Br. 512 A is A-1d and(R³)_(n) is 3,5-di-Br. 513 A is A-1d and (R³)_(n) is 3-I. 514 A is A-1dand (R³)_(n) is 2,5-di-I. 515 A is A-1d and (R³)_(n) is 3,5-di-I. 516 Ais A-1d and (R³)_(n) is 3-Me. 517 A is A-1d and (R³)_(n) is 2,5-di-Me.518 A is A-1d and (R³)_(n) is 3,5-di-Me. 519 A is A-1d and (R³)_(n) is3-Et. 520 A is A-1d and (R³)_(n) is 2,5-di-Et. 521 A is A-1d and(R³)_(n) is 3,5-di-Et. 522 A is A-1d and (R³)_(n) is 3-i-Pr. 523 A isA-1d and (R³)_(n) is 2,5-di-i-Pr. 524 A is A-1d and (R³)_(n) is3,5-di-i-Pr. 525 A is A-1d and (R³)_(n) is 3-c-Pr. 526 A is A-1d and(R³)_(n) is 2,5-di-c-Pr. 527 A is A-1d and (R³)_(n) is 3,5-di-c-Pr. 528A is A-1d and (R³)_(n) is 3-CF₃. 529 A is A-1d and (R³)_(n) is2,5-di-CF₃. 530 A is A-1d and (R³)_(n) is 3,5-di-CF₃. 531 A is A-1d and(R³)_(n) is 3-OMe. 532 A is A-1d and (R³)_(n) is 2,5-di-OMe. 533 A isA-1d and (R³)_(n) is 3,5-di-OMe. 534 A is A-1d and (R³)_(n) is 3-OCF₃.535 A is A-1d and (R³)_(n) is 2,5-di-OCF₃. 536 A is A-1d and (R³)_(n) is3,5-di-OCF₃. 537 A is A-1d and (R³)_(n) is 3-TMS. 538 A is A-1d and(R³)_(n) is 2,5-di-TMS. 539 A is A-1d and (R³)_(n) is 3,5-di-TMS. 540 Ais A-1d and (R³)_(n) is 2-Cl-6-Me. 541 A is A-1d and (R³)_(n) is2-Cl-5-Me. 542 A is A-1e and (R³)_(n) is 3-F. 543 A is A-1e and (R³)_(n)is 2,5-di-F. 544 A is A-1e and (R³)_(n) is 3,5-di-F. 545 A is A-1e and(R³)_(n) is 3-Cl. 546 A is A-1e and (R³)_(n) is 2,5-di-Cl. 547 A is A-1eand (R³)_(n) is 3,5-di-Cl. 548 A is A-1e and (R³)_(n) is 3-Br. 549 A isA-1e and (R³)_(n) is 2,5-di-Br. 550 A is A-1e and (R³)_(n) is 3,5-di-Br.551 A is A-1e and (R³)_(n) is 3-I. 552 A is A-1e and (R³)_(n) is2,5-di-I. 553 A is A-1e and (R³)_(n) is 3,5-di-I. 554 A is A-1e and(R³)_(n) is 3-Me. 555 A is A-1e and (R³)_(n) is 2,5-di-Me. 556 A is A-1eand (R³)_(n) is 3,5-di-Me. 557 A is A-1e and (R³)_(n) is 3-Et. 558 A isA-1e and (R³)_(n) is 2,5-di-Et. 559 A is A-1e and (R³)_(n) is 3,5-di-Et.560 A is A-1e and (R³)_(n) is 3-i-Pr. 561 A is A-1e and (R³)_(n) is2,5-di-i-Pr. 562 A is A-1e and (R³)_(n) is 3,5-di-i-Pr. 563 A is A-1eand (R³)_(n) is 3-c-Pr. 564 A is A-1e and (R³)_(n) is 2,5-di-c-Pr. 565 Ais A-1e and (R³)_(n) is 3,5-di-c-Pr. 566 A is A-1e and (R³)_(n) is3-CF₃. 567 A is A-1e and (R³)_(n) is 2,5-di-CF₃. 568 A is A-1e and(R³)_(n) is 3,5-di-CF₃. 569 A is A-1e and (R³)_(n) is 3-OMe. 570 A isA-1e and (R³)_(n) is 2,5-di-OMe. 571 A is A-1e and (R³)_(n) is3,5-di-OMe. 572 A is A-1e and (R³)_(n) is 3-OCF₃. 573 A is A-1e and(R³)_(n) is 2,5-di-OCF₃. 574 A is A-1e and (R³)_(n) is 3,5-di-OCF₃. 575A is A-1e and (R³)_(n) is 3-TMS. 576 A is A-1e and (R³)_(n) is2,5-di-TMS. 577 A is A-1e and (R³)_(n) is 3,5-di-TMS. 578 A is A-1e and(R³)_(n) is 2-Cl-6-Me. 579 A is A-1e and (R³)_(n) is 2-Cl-5-Me. 580 A isA-1f and (R³)_(n) is 3-F. 581 A is A-1f and (R³)_(n) is 2,5-di-F. 582 Ais A-1f and (R³)_(n) is 3,5-di-F. 583 A is A-1f and (R³)_(n) is 3-Cl.584 A is A-1f and (R³)_(n) is 2,5-di-Cl. 585 A is A-1f and (R³)_(n) is3,5-di-Cl. 586 A is A-1f and (R³)_(n) is 3-Br. 587 A is A-1f and(R³)_(n) is 2,5-di-Br. 588 A is A-1f and (R³)_(n) is 3,5-di-Br. 589 A isA-1f and (R³)_(n) is 3-I. 590 A is A-1f and (R³)_(n) is 2,5-di-I. 591 Ais A-1f and (R³)_(n) is 3,5-di-I. 592 A is A-1f and (R³)_(n) is 3-Me.593 A is A-1f and (R³)_(n) is 2,5-di-Me. 594 A is A-1f and (R³)_(n) is3,5-di-Me. 595 A is A-1f and (R³)_(n) is 2-Et. 596 A is A-1f and(R³)_(n) is 2,3-di-Et. 597 A is A-1f and (R³)_(n) is 2,6-di-Et. 598 A isA-1f and (R³)_(n) is 2-i-Pr. 599 A is A-1f and (R³)_(n) is 2,3-di-i-Pr.600 A is A-1f and (R³)_(n) is 2,6-di-i-Pr. 601 A is A-1f and (R³)_(n) is2-c-Pr. 602 A is A-1f and (R³)_(n) is 2,3-di-c-Pr. 603 A is A-1f and(R³)_(n) is 2,6-di-c-Pr. 604 A is A-1f and (R³)_(n) is 2-CF₃. 605 A isA-1f and (R³)_(n) is 2,3-di-CF₃. 606 A is A-1f and (R³)_(n) is2,6-di-CF₃. 607 A is A-1f and (R³)_(n) is 2-OMe. 608 A is A-1f and(R³)_(n) is 2,3-di-OMe. 609 A is A-1f and (R³)_(n) is 2,6-di-OMe. 610 Ais A-1f and (R³)_(n) is 2-OCF₃. 611 A is A-1f and (R³)_(n) is2,3-di-OCF₃. 612 A is A-1f and (R³)_(n) is 2,6-di-OCF₃. 613 A is A-1fand (R³)_(n) is 2-TMS. 614 A is A-1f and (R³)_(n) is 2,3-di-TMS. 615 Ais A-1f and (R³)_(n) is 2,6-di-TMS. 616 A is A-1f and (R³)_(n) is2-Cl-6-F. 617 A is A-1f and (R³)_(n) is 2-Cl-5-F. 618 A is A-1g and(R³)_(n) is 2-F. 619 A is A-1g and (R³)_(n) is 2,3-di-F. 620 A is A-1gand (R³)_(n) is 2,6-di-F. 621 A is A-1g and (R³)_(n) is 2-Cl. 622 A isA-1g and (R³)_(n) is 2,3-di-Cl. 623 A is A-1g and (R³)_(n) is 2,6-di-Cl.624 A is A-1g and (R³)_(n) is 2-Br. 625 A is A-1g and (R³)_(n) is2,3-di-Br. 626 A is A-1g and (R³)_(n) is 2,6-di-Br. 627 A is A-1g and(R³)_(n) is 2-I. 628 A is A-1g and (R³)_(n) is 2,3-di-I. 629 A is A-1gand (R³)_(n) is 2,6-di-I. 630 A is A-1g and (R³)_(n) is 2-Me. 631 A isA-1g and (R³)_(n) is 2,3-di-Me. 632 A is A-1g and (R³)_(n) is 2,6-di-Me.633 A is A-1g and (R³)_(n) is 2-Et. 634 A is A-1g and (R³)_(n) is2,3-di-Et. 635 A is A-1g and (R³)_(n) is 2,6-di-Et. 636 A is A-1g and(R³)_(n) is 2-i-Pr. 637 A is A-1g and (R³)_(n) is 2,3-di-i-Pr. 638 A isA-1g and (R³)_(n) is 2,6-di-i-Pr. 639 A is A-1g and (R³)_(n) is 2-c-Pr.640 A is A-1g and (R³)_(n) is 2,3-di-c-Pr. 641 A is A-1g and (R³)_(n) is2,6-di-c-Pr. 642 A is A-1g and (R³)_(n) is 2-CF₃. 643 A is A-1g and(R³)_(n) is 2,3-di-CF₃. 644 A is A-1g and (R³)_(n) is 2,6-di-CF₃. 645 Ais A-1g and (R³)_(n) is 2-OMe. 646 A is A-1g and (R³)_(n) is 2,3-di-OMe.647 A is A-1g and (R³)_(n) is 2,6-di-OMe. 648 A is A-1g and (R³)_(n) is2-OCF₃. 649 A is A-1g and (R³)_(n) is 2,3-di-OCF₃. 650 A is A-1g and(R³)_(n) is 2,6-di-OCF₃. 651 A is A-1g and (R³)_(n) is 2-TMS. 652 A isA-1g and (R³)_(n) is 2,3-di-TMS. 653 A is A-1g and (R³)_(n) is2,6-di-TMS. 654 A is A-1g and (R³)_(n) is 2-Cl-6-F. 655 A is A-1g and(R³)_(n) is 2-Cl-5-F. 656 A is A-1h and (R³)_(n) is 2-F. 657 A is A-1hand (R³)_(n) is 2,3-di-F. 658 A is A-1h and (R³)_(n) is 2,6-di-F. 659 Ais A-1h and (R³)_(n) is 2-Cl. 660 A is A-1h and (R³)_(n) is 2,3-di-Cl.661 A is A-1h and (R³)_(n) is 2,6-di-Cl. 662 A is A-1h and (R³)_(n) is2-Br. 663 A is A-1h and (R³)_(n) is 2,3-di-Br. 664 A is A-1h and(R³)_(n) is 2,6-di-Br. 665 A is A-1h and (R³)_(n) is 2-I. 666 A is A-1hand (R³)_(n) is 2,3-di-I. 667 A is A-1h and (R³)_(n) is 2,6-di-I. 668 Ais A-1h and (R³)_(n) is 2-Me. 669 A is A-1h and (R³)_(n) is 2,3-di-Me.670 A is A-1h and (R³)_(n) is 2,6-di-Me. 671 A is A-1h and (R³)_(n) is2-Et. 672 A is A-1h and (R³)_(n) is 2,3-di-Et. 673 A is A-1h and(R³)_(n) is 2,6-di-Et. 674 A is A-1h and (R³)_(n) is 2-i-Pr. 675 A isA-1h and (R³)_(n) is 2,3-di-i-Pr. 676 A is A-1h and (R³)_(n) is2,6-di-i-Pr. 677 A is A-1h and (R³)_(n) is 2-c-Pr. 678 A is A-1h and(R³)_(n) is 2,3-di-c-Pr. 679 A is A-1h and (R³)_(n) is 2,6-di-c-Pr. 680A is A-1h and (R³)_(n) is 2-CF₃. 681 A is A-1h and (R³)_(n) is2,3-di-CF₃. 682 A is A-1h and (R³)_(n) is 2,6-di-CF₃. 683 A is A-1h and(R³)_(n) is 2-OMe. 684 A is A-1h and (R³)_(n) is 2,3-di-OMe. 685 A isA-1h and (R³)_(n) is 2,6-di-OMe. 686 A is A-1h and (R³)_(n) is 2-OCF₃.687 A is A-1h and (R³)_(n) is 2,3-di-OCF₃. 688 A is A-1h and (R³)_(n) is2,6-di-OCF₃. 689 A is A-1h and (R³)_(n) is 2-TMS. 690 A is A-1h and(R³)_(n) is 2,3-di-TMS. 691 A is A-1h and (R³)_(n) is 2,6-di-TMS. 692 Ais A-1h and (R³)_(n) is 2-Cl-6-F. 693 A is A-1h and (R³)_(n) is2-Cl-5-F. 694 A is A-1i and (R³)_(n) is 2-F. 695 A is A-1i and (R³)_(n)is 2,3-di-F. 696 A is A-1i and (R³)_(n) is 2,6-di-F. 697 A is A-1i and(R³)_(n) is 2-Cl. 698 A is A-1i and (R³)_(n) is 2,3-di-Cl. 699 A is A-1iand (R³)_(n) is 2,6-di-Cl. 700 A is A-1i and (R³)_(n) is 2-Br. 701 A isA-1i and (R³)_(n) is 2,3-di-Br. 702 A is A-1i and (R³)_(n) is 2,6-di-Br.703 A is A-1i and (R³)_(n) is 2-I. 704 A is A-1i and (R³)_(n) is2,3-di-I. 705 A is A-1i and (R³)_(n) is 2,6-di-I. 706 A is A-1i and(R³)_(n) is 2-Me. 707 A is A-1i and (R³)_(n) is 2,3-di-Me. 708 A is A-1iand (R³)_(n) is 2,6-di-Me. 709 A is A-1i and (R³)_(n) is 2-Et. 710 A isA-1i and (R³)_(n) is 2,3-di-Et. 711 A is A-1i and (R³)_(n) is 2,6-di-Et.712 A is A-1i and (R³)_(n) is 2-i-Pr. 713 A is A-1i and (R³)_(n) is2,3-di-i-Pr. 714 A is A-1i and (R³)_(n) is 2,6-di-i-Pr. 715 A is A-1iand (R³)_(n) is 2-c-Pr. 716 A is A-1i and (R³)_(n) is 2,3-di-c-Pr. 717 Ais A-1i and (R³)_(n) is 2,6-di-c-Pr. 718 A is A-1i and (R³)_(n) is2-CF₃. 719 A is A-1i and (R³)_(n) is 2,3-di-CF₃. 720 A is A-1i and(R³)_(n) is 2,6-di-CF₃. 721 A is A-1i and (R³)_(n) is 2-OMe. 722 A isA-1i and (R³)_(n) is 2,3-di-OMe. 723 A is A-1i and (R³)_(n) is2,6-di-OMe. 724 A is A-1i and (R³)_(n) is 2-OCF₃. 725 A is A-1i and(R³)_(n) is 2,3-di-OCF₃. 726 A is A-1i and (R³)_(n) is 2,6-di-OCF₃. 727A is A-1i and (R³)_(n) is 2-TMS. 728 A is A-1i and (R³)_(n) is2,3-di-TMS. 729 A is A-1i and (R³)_(n) is 2,6-di-TMS. 730 A is A-1i and(R³)_(n) is 2-Cl-6-F. 731 A is A-1i and (R³)_(n) is 2-Cl-5-F. 732 A isA-1j and (R³)_(n) is 2-F. 733 A is A-1j and (R³)_(n) is 2,3-di-F. 734 Ais A-1j and (R³)_(n) is 2,6-di-F. 735 A is A-1j and (R³)_(n) is 2-Cl.736 A is A-1j and (R³)_(n) is 2,3-di-Cl. 737 A is A-1j and (R³)_(n) is2,6-di-Cl. 738 A is A-1j and (R³)_(n) is 2-Br. 739 A is A-1j and(R³)_(n) is 2,3-di-Br. 740 A is A-1j and (R³)_(n) is 2,6-di-Br. 741 A isA-1j and (R³)_(n) is 2-I. 742 A is A-1j and (R³)_(n) is 2,3-di-I. 743 Ais A-1j and (R³)_(n) is 2,6-di-I. 744 A is A-1j and (R³)_(n) is 2-Me.745 A is A-1j and (R³)_(n) is 2,3-di-Me. 746 A is A-1j and (R³)_(n) is2,6-di-Me. 747 A is A-1j and (R³)_(n) is 2-Et. 748 A is A-1j and(R³)_(n) is 2,3-di-Et. 749 A is A-1j and (R³)_(n) is 2,6-di-Et. 750 A isA-1j and (R³)_(n) is 2-i-Pr. 751 A is A-1j and (R³)_(n) is 2,3-di-i-Pr.752 A is A-1j and (R³)_(n) is 2,6-di-i-Pr. 753 A is A-1j and (R³)_(n) is2-c-Pr. 754 A is A-1j and (R³)_(n) is 2,3-di-c-Pr. 755 A is A-1j and(R³)_(n) is 2,6-di-c-Pr. 756 A is A-1j and (R³)_(n) is 2-CF₃. 757 A isA-1j and (R³)_(n) is 2,3-di-CF₃. 758 A is A-1j and (R³)_(n) is2,6-di-CF₃. 759 A is A-1j and (R³)_(n) is 2-OMe. 760 A is A-1j and(R³)_(n) is 2,3-di-OMe. 761 A is A-1j and (R³)_(n) is 2,6-di-OMe. 762 Ais A-1j and (R³)_(n) is 2-OCF₃. 763 A is A-1j and (R³)_(n) is2,3-di-OCF₃. 764 A is A-1j and (R³)_(n) is 2,6-di-OCF₃. 765 A is A-1jand (R³)_(n) is 2-TMS. 766 A is A-1j and (R³)_(n) is 2,3-di-TMS. 767 Ais A-1j and (R³)_(n) is 2,6-di-TMS. 768 A is A-1j and (R³)_(n) is2-Cl-6-F. 769 A is A-1j and (R³)_(n) is 2-Cl-5-F.

TABLE 770

A is A-1a, (R³)_(n) is H. Q 3-CF₃-1H-pyrazol-1-yl 3-Br-1H-pyrazol-1-yl4-F-1H-pyrazol-1-yl 5-Me-1H-pyrazol-1-yl 3-CHF₂-1H-pyrazol-1-yl3-I-1H-pyrazol-1-yl 4-Cl-1H-pyrazol-1-yl 5-Et-1H-pyrazol-1-yl3-OMe-1H-pyrazol-1-yl 3-OCHF₂-1H-pyrazol-1-yl 4-OCF₃-1H-pyrazol-1-yl5-CN-1H-pyrazol-1-yl 3-MeOC(═O)-1H-pyrazol-1-yl 3,5-di-F-1H-pyrazol-1-yl3,5-di-CF₃-1H-pyrazol-1-yl 5-Ph-1H-pyrazol-1-yl3-CF₃-5-Me-1H-pyrazol-1-yl 3,4-di-Br-1H-pyrazol-1-yl3-Me-1H-[1,2,4]triazol-1-yl 3-F-1H-[1,2,4]triazol-1-yl3,5-di-Cl-1H-[1,2,4]triazol-1-yl 1H-[1,2,4]triazol-1-yl4-CHF₂-2H-[1,2,3]triazol-2-yl 4-Br-2H-[1,2,3]triazol-2-yl4,5-di-CF₃-2H-[1,2,3]triazol-2-yl 2H-[1,2,3]triazol-2-yl4-CHF₂-1H-[1,2,3]triazol-1-yl 4-Br-1H-[1,2,3]triazol-1-yl3-Me-1H-pyrrol-1-yl 3,4-di-Me-1H-pyrrol-1-yl 2,4-di-CF₃-1H-pyrrol-1-yl1H-pyrrol-1-yl 1-Et-1H-pyrazol-3-yl 1-Ph-1H-pyrazol-3-yl1-Me-1H-pyrazol-4-yl 1-i-Pr-1H-pyrazol-4-yl 1,3-di-Me-1H-pyrazol-4-yl1-Me-1H-[1,2,4]triazol-3-yl 1-i-Pr-1H-[1,2,4]triazol-3-yl3,5-di-Me-1H-[1,2,4]triazol-1-yl 5-CF₃-2,4-dihydro-3-oxopyrazol-1-yl3-Me-1H-pyrazol-1-yl 4-CF₃-1H-pyrazol-1-yl 4-Br-1H-pyrazol-1-yl5-F-1H-pyrazol-1-yl 3-Et-1H-pyrazol-1-yl 4-CHF₂-1H-pyrazol-1-yl4-I-1H-pyrazol-1-yl 5-Cl-1H-pyrazol-1-yl 3-CN-1H-pyrazol-1-yl4-OMe-1H-pyrazol-1-yl 4-OCHF₂-1H-pyrazol-1-yl 5-OCF₃-1H-pyrazol-1-yl3-Ph-1H-pyrazol-1-yl 4-MeOC(═O)-1H-pyrazol-1-yl3,5-di-Cl-1H-pyrazol-1-yl 3,5-di-CHF₂-1H-pyrazol-1-yl3,4-di-Me-1H-pyrazol-1-yl 3,4-di-Cl-1H-pyrazol-1-yl3-CF₃-1H-[1,2,4]triazol-1-yl 3-Cl-1H-[1,2,4]triazol-1-yl3,5-di-Br-1H-[1,2,4]triazol-1-yl 4-Me-2H-[1,2,3]triazol-2-yl4-F-2H-[1,2,3]triazol-2-yl 4-Ph-2H-[1,2,3]triazol-2-yl4,5-di-Cl-2H-[1,2,3]triazol-2-yl 4-Me-1H-[1,2,3]triazol-1-yl4-F-1H-[1,2,3]triazol-1-yl 4-Ph-1H-[1,2,3]triazol-1-yl3-CF₃-1H-pyrrol-1-yl 2,4-di-Me-1H-pyrrol-1-yl 3,4-di-Br-1H-pyrrol-1-yl1-Me-1H-pyrazol-3-yl 1-i-Pr-1H-pyrazol-3-yl 1,4-di-Me-1H-pyrazol-3-yl1-CF₃-1H-pyrazol-4-yl 1-(F₃CCH₂)-1H-pyrazol-4-yl1-Me-3-CF3-1H-pyrazol-4-yl 1-CF₃-1H-[1,2,4]triazol-3-yl1-Ph-1H-[1,2,4]triazol-3-yl 3,5-di-CF₃-1H-[1,2,4]triazol-1-yl5-Me-2,4-dihydro-3-oxopyrazol-1-yl 3-F-1H-pyrazol-1-yl4-Me-1H-pyrazol-1-yl 5-CF₃-1H-pyrazol-1-yl 5-Br-1H-pyrazol-1-yl3-Cl-1H-pyrazol-1-yl 4-Et-1H-pyrazol-1-yl 5-CHF₂-1H-pyrazol-1-yl3-I-1H-pyrazol-1-yl 3-OCF₃-1H-pyrazol-1-yl 4-CN-1H-pyrazol-1-yl5-OCF₃-1H-pyrazol-1-yl 5-OCHF₂-1H-pyrazol-1-yl 3,5-di-Me-1H-pyrazol-1-yl4-Ph-1H-pyrazol-1-yl 5-MeOC(═O)-1H-pyrazol-1-yl3,5-di-Br-1H-pyrazol-1-yl 3,4-di-CF₃-1H-pyrazol-1-yl 1H-pyrazol-1-yl3-CHF₂-1H-[1,2,4]triazol-1-yl 3-Br-1H-[1,2,4]triazol-1-yl3-Ph-1H-[1,2,4]triazol-1-yl 4-CF₃-2H-[1,2,3]triazol-2-yl4-Cl-2H-[1,2,3]triazol-2-yl 4,5-di-Me-2H-[1,2,3]triazol-2-yl4,5-di-Br-2H-[1,2,3]triazol-2-yl 4-CF₃-1H-[1,2,3]triazol-1-yl4-Cl-1H-[1,2,3]triazol-1-yl 1H-[1,2,3]triazol-1-yl 3-CHF₂-1H-pyrrol-1-yl3,4-di-CF₃-1H-pyrrol-1-yl 3,4-di-Cl-1H-pyrrol-1-yl 1-CF₃-1H-pyrazol-3-yl1-(F₃CCH₂)-1H-pyrazol-3-yl 1-Me-4-CF₃-1H-pyrazol-3-yl1-Et-1H-pyrazol-4-yl 1-Ph-1H-pyrazol-4-yl 3-Me-1-CF₃-1H-pyrazol-4-yl1-Et-1H-[1,2,4]triazol-3-yl 5-Ph-4,5-dihydro-isoxazol-3-yl3,5-di-CHF₂-1H-[1,2,4]triazol-1-yl

The present disclosure also includes Tables 771 through 1539, each ofwhich is constructed the same as Table 770 above, except that the rowheading in Table 771 (i.e. “A is A-1a and R³ is H.”) is replaced withthe respective row heading shown below. For Example, in Table 771 therow heading is “A is A-1a and R³ is 2-F” and Q is as defined in Table 1above. Thus, the first entry in Table 771 specifically disclosesN-[[2-fluoro-3-(3-trifluoromethyl-1H-pyrazol-1-yl)phenyl]methyl]-N-cyclopropyl-3-(trifluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide.Tables 772 through 1539 are constructed similarly.

TABLES 771-1539 Table Row Heading 771 A is A-1a and (R³)_(n) is 2-F. 772A is A-1a and (R³)_(n) is 2,4-di-F. 773 A is A-1a and (R³)_(n) is2,6-di-F. 774 A is A-1a and (R³)_(n) is 2-Cl. 775 A is A-1a and (R³)_(n)is 2,4-di-Cl. 776 A is A-1a and (R³)_(n) is 2,6-di-Cl. 777 A is A-1a and(R³)_(n) is 2-Br. 778 A is A-1a and (R³)_(n) is 2,4-di-Br. 779 A is A-1aand (R³)_(n) is 2,6-di-Br. 780 A is A-1a and (R³)_(n) is 2-I. 781 A isA-1a and (R³)_(n) is 2,4-di-I. 782 A is A-1a and (R³)_(n) is 2,6-di-I.783 A is A-1a and (R³)_(n) is 2-Me. 784 A is A-1a and (R³)_(n) is2,4-di-Me. 785 A is A-1a and (R³)_(n) is 2,6-di-Me. 786 A is A-1a and(R³)_(n) is 2-Et. 787 A is A-1a and (R³)_(n) is 2,4-di-Et. 788 A is A-1aand (R³)_(n) is 2,6-di-Et. 789 A is A-1a and (R³)_(n) is 2-i-Pr. 790 Ais A-1a and (R³)_(n) is 2,4-di-i-Pr. 791 A is A-1a and (R³)_(n) is2,6-di-i-Pr. 792 A is A-1a and (R³)_(n) is 2-c-Pr. 793 A is A-1a and(R³)_(n) is 2,4-di-c-Pr. 794 A is A-1a and (R³)_(n) is 2,6-di-c-Pr. 795A is A-1a and (R³)_(n) is 2-CF₃. 796 A is A-1a and (R³)_(n) is2,4-di-CF₃. 797 A is A-1a and (R³)_(n) is 2,6-di-CF₃. 798 A is A-1a and(R³)_(n) is 2-OMe. 799 A is A-1a and (R³)_(n) is 2,4-di-OMe. 800 A isA-1a and (R³)_(n) is 2,6-di-OMe. 801 A is A-1a and (R³)_(n) is 2-OCF3.802 A is A-1a and (R³)_(n) is 2,4-di-OCF₃. 803 A is A-1a and (R³)_(n) is2,6-di-OCF₃. 804 A is A-1a and (R³)_(n) is 2-TMS. 805 A is A-1a and(R³)_(n) is 2,4-di-TMS. 806 A is A-1a and (R³)_(n) is 2,6-di-TMS. 807 Ais A-1a and (R³)_(n) is 2-Cl-6-F. 808 A is A-1a and (R³)_(n) is2-Cl-4-F. 809 A is A-1b and (R³)_(n) is H. 810 A is A-1b and (R³)_(n) is2-F. 811 A is A-1b and (R³)_(n) is 2,4-di-F. 812 A is A-1b and (R³)_(n)is 2,6-di-F. 813 A is A-1b and (R³)_(n) is 2-Cl. 814 A is A-1b and(R³)_(n) is 2,4-di-Cl. 815 A is A-1b and (R³)_(n) is 2,6-di-Cl. 816 A isA-1b and (R³)_(n) is 2-Br. 817 A is A-1b and (R³)_(n) is 2,4-di-Br. 818A is A-1b and (R³)_(n) is 2,6-di-Br. 819 A is A-1b and (R³)_(n) is 2-I.820 A is A-1b and (R³)_(n) is 2,4-di-I. 821 A is A-1b and (R³)_(n) is2,6-di-I. 822 A is A-1b and (R³)_(n) is 2-Me. 823 A is A-1b and (R³)_(n)is 2,4-di-Me. 824 A is A-1b and (R³)_(n) is 2,6-di-Me. 825 A is A-1b and(R³)_(n) is 2-Et. 826 A is A-1b and (R³)_(n) is 2,4-di-Et. 827 A is A-1band (R³)_(n) is 2,6-di-Et. 828 A is A-1b and (R³)_(n) is 2-i-Pr. 829 Ais A-1b and (R³)_(n) is 2,4-di-i-Pr. 830 A is A-1b and (R³)_(n) is2,6-di-i-Pr. 831 A is A-1b and (R³)_(n) is 2-c-Pr. 832 A is A-1b and(R³)_(n) is 2,4-di-c-Pr. 833 A is A-1b and (R³)_(n) is 2,6-di-c-Pr. 834A is A-1b and (R³)_(n) is 2-CF₃. 835 A is A-1b and (R³)_(n) is2,4-di-CF₃. 836 A is A-1b and (R³)_(n) is 2,6-di-CF₃. 837 A is A-1b and(R³)_(n) is 2-OMe. 838 A is A-1b and (R³)_(n) is 2,4-di-OMe. 839 A isA-1b and (R³)_(n) is 2,6-di-OMe. 840 A is A-1b and (R³)_(n) is 2-OCF₃.841 A is A-1b and (R³)_(n) is 2,4-di-OCF₃. 842 A is A-1b and (R³)_(n) is2,6-di-OCF₃. 843 A is A-1b and (R³)_(n) is 2-TMS. 844 A is A-1b and(R³)_(n) is 2,4-di-TMS. 845 A is A-1b and (R³)_(n) is 2,6-di-TMS. 846 Ais A-1b and (R³)_(n) is 2-Cl-6-F. 847 A is A-1b and (R³)_(n) is2-Cl-4-F. 848 A is A-1c and (R³)_(n) is H. 849 A is A-1c and (R³)_(n) is2-F. 850 A is A-1c and (R³)_(n) is 2,4-di-F. 851 A is A-1c and (R³)_(n)is 2,6-di-F. 852 A is A-1c and (R³)_(n) is 2-Cl. 853 A is A-1c and(R³)_(n) is 2,4-di-Cl. 854 A is A-1c and (R³)_(n) is 2,6-di-Cl. 855 A isA-1c and (R³)_(n) is 2-Br. 856 A is A-1c and (R³)_(n) is 2,4-di-Br. 857A is A-1c and (R³)_(n) is 2,6-di-Br. 858 A is A-1c and (R³)_(n) is 2-I.859 A is A-1c and (R³)_(n) is 2,4-di-I. 860 A is A-1c and (R³)_(n) is2,6-di-I. 861 A is A-1c and (R³)_(n) is 2-Me. 862 A is A-1c and (R³)_(n)is 2,4-di-Me. 863 A is A-1c and (R³)_(n) is 2,6-di-Me. 864 A is A-1c and(R³)_(n) is 2-Et. 865 A is A-1c and (R³)_(n) is 2,4-di-Et. 866 A is A-1cand (R³)_(n) is 2,6-di-Et. 867 A is A-1c and (R³)_(n) is 2-i-Pr. 868 Ais A-1c and (R³)_(n) is 2,4-di-i-Pr. 869 A is A-1c and (R³)_(n) is2,6-di-i-Pr. 870 A is A-1c and (R³)_(n) is 2-c-Pr. 871 A is A-1c and(R³)_(n) is 2,4-di-c-Pr. 872 A is A-1c and (R³)_(n) is 2,6-di-c-Pr. 873A is A-1c and (R³)_(n) is 2-CF₃. 874 A is A-1c and (R³)_(n) is2,4-di-CF₃. 875 A is A-1c and (R³)_(n) is 2,6-di-CF₃. 876 A is A-1c and(R³)_(n) is 2-OMe. 877 A is A-1c and (R³)_(n) is 2,4-di-OMe. 878 A isA-1c and (R³)_(n) is 2,6-di-OMe. 879 A is A-1c and (R³)_(n) is 2-OCF3.880 A is A-1c and (R³)_(n) is 2,4-di-OCF₃. 881 A is A-1c and (R³)_(n) is2,6-di-OCF₃. 882 A is A-1c and (R³)_(n) is 2-TMS. 883 A is A-1c and(R³)_(n) is 2,4-di-TMS. 884 A is A-1c and (R³)_(n) is 2,6-di-TMS. 885 Ais A-1c and (R³)_(n) is 2-Cl-6-F. 886 A is A-1c and (R³)_(n) is2-Cl-4-F. 887 A is A-1d and (R³)_(n) is H. 888 A is A-1d and (R³)_(n) is2-F. 889 A is A-1d and (R³)_(n) is 2,4-di-F. 890 A is A-1d and (R³)_(n)is 2,6-di-F. 891 A is A-1d and (R³)_(n) is 2-Cl. 892 A is A-1d and(R³)_(n) is 2,4-di-Cl. 893 A is A-1d and (R³)_(n) is 2,6-di-Cl. 894 A isA-1d and (R³)_(n) is 2-Br. 895 A is A-1d and (R³)_(n) is 2,4-di-Br. 896A is A-1d and (R³)_(n) is 2,6-di-Br. 897 A is A-1d and (R³)_(n) is 2-I.898 A is A-1d and (R³)_(n) is 2,4-di-I. 899 A is A-1d and (R³)_(n) is2,6-di-I. 900 A is A-1d and (R³)_(n) is 2-Me. 901 A is A-1d and (R³)_(n)is 2,4-di-Me. 902 A is A-1d and (R³)_(n) is 2,6-di-Me. 903 A is A-1d and(R³)_(n) is 2-Et. 904 A is A-1d and (R³)_(n) is 2,4-di-Et. 905 A is A-1dand (R³)_(n) is 2,6-di-Et. 906 A is A-1d and (R³)_(n) is 2-i-Pr. 907 Ais A-1d and (R³)_(n) is 2,4-di-i-Pr. 908 A is A-1d and (R³)_(n) is2,6-di-i-Pr. 909 A is A-1d and (R³)_(n) is 2-c-Pr. 910 A is A-1d and(R³)_(n) is 2,4-di-c-Pr. 911 A is A-1d and (R³)_(n) is 2,6-di-c-Pr. 912A is A-1d and (R³)_(n) is 2-CF₃. 913 A is A-1d and (R³)_(n) is2,4-di-CF₃. 914 A is A-1d and (R³)_(n) is 2,6-di-CF₃. 915 A is A-1d and(R³)_(n) is 2-OMe. 916 A is A-1d and (R³)_(n) is 2,4-di-OMe. 917 A isA-1d and (R³)_(n) is 2,6-di-OMe. 918 A is A-1d and (R³)_(n) is 2-OCF₃.919 A is A-1d and (R³)_(n) is 2,4-di-OCF₃. 920 A is A-1d and (R³)_(n) is2,6-di-OCF₃. 921 A is A-1d and (R³)_(n) is 2-TMS. 922 A is A-1d and(R³)_(n) is 2,4-di-TMS. 923 A is A-1d and (R³)_(n) is 2,6-di-TMS. 924 Ais A-1d and (R³)_(n) is 2-Cl-6-F. 925 A is A-1d and (R³)_(n) is2-Cl-4-F. 926 A is A-1e and (R³)_(n) is H. 927 A is A-1e and (R³)_(n) is2-F. 928 A is A-1e and (R³)_(n) is 2,4-di-F. 929 A is A-1e and (R³)_(n)is 2,6-di-F. 930 A is A-1e and (R³)_(n) is 2-Cl. 931 A is A-1e and(R³)_(n) is 2,4-di-Cl. 932 A is A-1e and (R³)_(n) is 2,6-di-Cl. 933 A isA-1e and (R³)_(n) is 2-Br. 934 A is A-1e and (R³)_(n) is 2,4-di-Br. 935A is A-1e and (R³)_(n) is 2,6-di-Br. 936 A is A-1e and (R³)_(n) is 2-I.937 A is A-1e and (R³)_(n) is 2,4-di-I. 938 A is A-1e and (R³)_(n) is2,6-di-I. 939 A is A-1e and (R³)_(n) is 2-Me. 940 A is A-1e and (R³)_(n)is 2,4-di-Me. 941 A is A-1e and (R³)_(n) is 2,6-di-Me. 942 A is A-1e and(R³)_(n) is 2-Et. 943 A is A-1e and (R³)_(n) is 2,4-di-Et. 944 A is A-1eand (R³)_(n) is 2,6-di-Et. 945 A is A-1e and (R³)_(n) is 2-i-Pr. 946 Ais A-1e and (R³)_(n) is 2,4-di-i-Pr. 947 A is A-1e and (R³)_(n) is2,6-di-i-Pr. 948 A is A-1e and (R³)_(n) is 2-c-Pr. 949 A is A-1e and(R³)_(n) is 2,4-di-c-Pr. 950 A is A-1e and (R³)_(n) is 2,6-di-c-Pr. 951A is A-1e and (R³)_(n) is 2-CF₃. 952 A is A-1e and (R³)_(n) is2,4-di-CF₃. 953 A is A-1e and (R³)_(n) is 2,6-di-CF₃. 954 A is A-1e and(R³)_(n) is 2-OMe. 955 A is A-1e and (R³)_(n) is 2,4-di-OMe. 956 A isA-1e and (R³)_(n) is 2,6-di-OMe. 957 A is A-1e and (R³)_(n) is 2-OCF₃.958 A is A-1e and (R³)_(n) is 2,4-di-OCF₃. 959 A is A-1e and (R³)_(n) is2,6-di-OCF₃. 960 A is A-1e and (R³)_(n) is 2-TMS. 961 A is A-1e and(R³)_(n) is 2,4-di-TMS. 962 A is A-1e and (R³)_(n) is 2,6-di-TMS. 963 Ais A-1e and (R³)_(n) is 2-Cl-6-F. 964 A is A-1e and (R³)_(n) is2-Cl-4-F. 965 A is A-1f and (R³)_(n) is H. 966 A is A-1f and (R³)_(n) is2-F. 967 A is A-1f and (R³)_(n) is 2,4-di-F. 968 A is A-1f and (R³)_(n)is 2,6-di-F. 969 A is A-1f and (R³)_(n) is 2-Cl. 970 A is A-1f and(R³)_(n) is 2,4-di-Cl. 971 A is A-1f and (R³)_(n) is 2,6-di-Cl. 972 A isA-1f and (R³)_(n) is 2-Br. 973 A is A-1f and (R³)_(n) is 2,4-di-Br. 974A is A-1f and (R³)_(n) is 2,6-di-Br. 975 A is A-1f and (R³)_(n) is 2-I.976 A is A-1f and (R³)_(n) is 2,4-di-I. 977 A is A-1f and (R³)_(n) is2,6-di-I. 978 A is A-1f and (R³)_(n) is 2-Me. 979 A is A-1f and (R³)_(n)is 2,4-di-Me. 980 A is A-1f and (R³)_(n) is 2,6-di-Me. 981 A is A-1f and(R³)_(n) is 2-Et. 982 A is A-1f and (R³)_(n) is 2,4-di-Et. 983 A is A-1fand (R³)_(n) is 2,6-di-Et. 984 A is A-1f and (R³)_(n) is 2-i-Pr. 985 Ais A-1f and (R³)_(n) is 2,4-di-i-Pr. 986 A is A-1f and (R³)_(n) is2,6-di-i-Pr. 987 A is A-1f and (R³)_(n) is 2-c-Pr. 988 A is A-1f and(R³)_(n) is 2,4-di-c-Pr. 989 A is A-1f and (R³)_(n) is 2,6-di-c-Pr. 990A is A-1f and (R³)_(n) is 2-CF₃. 991 A is A-1f and (R³)_(n) is2,4-di-CF₃. 992 A is A-1f and (R³)_(n) is 2,6-di-CF₃. 993 A is A-1f and(R³)_(n) is 2-OMe. 994 A is A-1f and (R³)_(n) is 2,4-di-OMe. 995 A isA-1f and (R³)_(n) is 2,6-di-OMe. 996 A is A-1f and (R³)_(n) is 2-OCF₃.997 A is A-1f and (R³)_(n) is 2,4-di-OCF₃. 998 A is A-1f and (R³)_(n) is2,6-di-OCF₃. 999 A is A-1f and (R³)_(n) is 2-TMS. 1000 A is A-1f and(R³)_(n) is 2,4-di-TMS. 1001 A is A-1f and (R³)_(n) is 2,6-di-TMS. 1002A is A-1f and (R³)_(n) is 2-Cl-6-F. 1003 A is A-1f and (R³)_(n) is2-Cl-4-F. 1004 A is A-1g and (R³)_(n) is H. 1005 A is A-1g and (R³)_(n)is 2-F. 1006 A is A-1g and (R³)_(n) is 2,4-di-F. 1007 A is A-1g and(R³)_(n) is 2,6-di-F. 1008 A is A-1g and (R³)_(n) is 2-Cl. 1009 A isA-1g and (R³)_(n) is 2,4-di-Cl. 1010 A is A-1g and (R³)_(n) is2,6-di-Cl. 1011 A is A-1g and (R³)_(n) is 2-Br. 1012 A is A-1g and(R³)_(n) is 2,4-di-Br. 1013 A is A-1g and (R³)_(n) is 2,6-di-Br. 1014 Ais A-1g and (R³)_(n) is 2-I. 1015 A is A-1g and (R³)_(n) is 2,4-di-I.1016 A is A-1g and (R³)_(n) is 2,6-di-I. 1017 A is A-1g and (R³)_(n) is2-Me. 1018 A is A-1g and (R³)_(n) is 2,4-di-Me. 1019 A is A-1g and(R³)_(n) is 2,6-di-Me. 1020 A is A-1g and (R³)_(n) is 2-Et. 1021 A isA-1g and (R³)_(n) is 2,4-di-Et. 1022 A is A-1g and (R³)_(n) is2,6-di-Et. 1023 A is A-1g and (R³)_(n) is 2-i-Pr. 1024 A is A-1g and(R³)_(n) is 2,4-di-i-Pr. 1025 A is A-1g and (R³)_(n) is 2,6-di-i-Pr.1026 A is A-1g and (R³)_(n) is 2-c-Pr. 1027 A is A-1g and (R³)_(n) is2,4-di-c-Pr. 1028 A is A-1g and (R³)_(n) is 2,6-di-c-Pr. 1029 A is A-1gand (R³)_(n) is 2-CF₃. 1030 A is A-1g and (R³)_(n) is 2,4-di-CF₃. 1031 Ais A-1g and (R³)_(n) is 2,6-di-CF₃. 1032 A is A-1g and (R³)_(n) is2-OMe. 1033 A is A-1g and (R³)_(n) is 2,4-di-OMe. 1034 A is A-1g and(R³)_(n) is 2,6-di-OMe. 1035 A is A-1g and (R³)_(n) is 2-OCF₃. 1036 A isA-1g and (R³)_(n) is 2,4-di-OCF₃. 1037 A is A-1g and (R³)_(n) is2,6-di-OCF₃. 1038 A is A-1g and (R³)_(n) is 2-TMS. 1039 A is A-1g and(R³)_(n) is 2,4-di-TMS. 1040 A is A-1g and (R³)_(n) is 2,6-di-TMS. 1041A is A-1g and (R³)_(n) is 2-Cl-6-F. 1042 A is A-1g and (R³)_(n) is2-Cl-4-F. 1043 A is A-1h and (R³)_(n) is H. 1044 A is A-1h and (R³)_(n)is 2-F. 1045 A is A-1h and (R³)_(n) is 2,4-di-F. 1046 A is A-1h and(R³)_(n) is 2,6-di-F. 1047 A is A-1h and (R³)_(n) is 2-Cl. 1048 A isA-1h and (R³)_(n) is 2,4-di-Cl. 1049 A is A-1h and (R³)_(n) is2,6-di-Cl. 1050 A is A-1h and (R³)_(n) is 2-Br. 1051 A is A-1h and(R³)_(n) is 2,4-di-Br. 1052 A is A-1h and (R³)_(n) is 2,6-di-Br. 1053 Ais A-1h and (R³)_(n) is 2-I. 1054 A is A-1h and (R³)_(n) is 2,4-di-I.1055 A is A-1h and (R³)_(n) is 2,6-di-I. 1056 A is A-1h and (R³)_(n) is2-Me. 1057 A is A-1h and (R³)_(n) is 2,4-di-Me. 1058 A is A-1h and(R³)_(n) is 2,6-di-Me. 1059 A is A-1h and (R³)_(n) is 2-Et. 1060 A isA-1h and (R³)_(n) is 2,4-di-Et. 1061 A is A-1h and (R³)_(n) is2,6-di-Et. 1062 A is A-1h and (R³)_(n) is 2-i-Pr. 1063 A is A-1h and(R³)_(n) is 2,4-di-i-Pr. 1064 A is A-1h and (R³)_(n) is 2,6-di-i-Pr.1065 A is A-1h and (R³)_(n) is 2-c-Pr. 1066 A is A-1h and (R³)_(n) is2,4-di-c-Pr. 1067 A is A-1h and (R³)_(n) is 2,6-di-c-Pr. 1068 A is A-1hand (R³)_(n) is 2-CF₃. 1069 A is A-1h and (R³)_(n) is 2,4-di-CF₃. 1070 Ais A-1h and (R³)_(n) is 2,6-di-CF₃. 1071 A is A-1h and (R³)_(n) is2-OMe. 1072 A is A-1h and (R³)_(n) is 2,4-di-OMe. 1073 A is A-1h and(R³)_(n) is 2,6-di-OMe. 1074 A is A-1h and (R³)_(n) is 2-OCF₃. 1075 A isA-1h and (R³)_(n) is 2,4-di-OCF₃. 1076 A is A-1h and (R³)_(n) is2,6-di-OCF₃. 1077 A is A-1h and (R³)_(n) is 2-TMS. 1078 A is A-1h and(R³)_(n) is 2,4-di-TMS. 1079 A is A-1h and (R³)_(n) is 2,6-di-TMS. 1080A is A-1h and (R³)_(n) is 2-Cl-6-F. 1081 A is A-1h and (R³)_(n) is2-Cl-4-F. 1082 A is A-1i and (R³)_(n) is H. 1083 A is A-1i and (R³)_(n)is 2-F. 1084 A is A-1i and (R³)_(n) is 2,4-di-F. 1085 A is A-1i and(R³)_(n) is 2,6-di-F. 1086 A is A-1i and (R³)_(n) is 2-Cl. 1087 A isA-1i and (R³)_(n) is 2,4-di-Cl. 1088 A is A-1i and (R³)_(n) is2,6-di-Cl. 1089 A is A-1i and (R³)_(n) is 2-Br. 1090 A is A-1i and(R³)_(n) is 2,4-di-Br. 1091 A is A-1i and (R³)_(n) is 2,6-di-Br. 1092 Ais A-1i and (R³)_(n) is 2-I. 1093 A is A-1i and (R³)_(n) is 2,4-di-I.1094 A is A-1i and (R³)_(n) is 2,6-di-I. 1095 A is A-1i and (R³)_(n) is2-Me. 1096 A is A-1i and (R³)_(n) is 2,4-di-Me. 1097 A is A-1i and(R³)_(n) is 2,6-di-Me. 1098 A is A-1i and (R³)_(n) is 2-Et. 1099 A isA-1i and (R³)_(n) is 2,4-di-Et. 1100 A is A-1i and (R³)_(n) is2,6-di-Et. 1101 A is A-1i and (R³)_(n) is 2-i-Pr. 1102 A is A-1i and(R³)_(n) is 2,4-di-i-Pr. 1103 A is A-1i and (R³)_(n) is 2,6-di-i-Pr.1104 A is A-1i and (R³)_(n) is 2-c-Pr. 1105 A is A-1i and (R³)_(n) is2,4-di-c-Pr. 1106 A is A-1i and (R³)_(n) is 2,6-di-c-Pr. 1107 A is A-1iand (R³)_(n) is 2-CF₃. 1108 A is A-1i and (R³)_(n) is 2,4-di-CF₃. 1109 Ais A-1i and (R³)_(n) is 2,6-di-CF₃. 1110 A is A-1i and (R³)_(n) is2-OMe. 1111 A is A-1i and (R³)_(n) is 2,4-di-OMe. 1112 A is A-1i and(R³)_(n) is 2,6-di-OMe. 1113 A is A-1i and (R³)_(n) is 2-OCF₃. 1114 A isA-1i and (R³)_(n) is 2,4-di-OCF₃. 1115 A is A-1i and (R³)_(n) is2,6-di-OCF₃. 1116 A is A-1i and (R³)_(n) is 2-TMS. 1117 A is A-1i and(R³)_(n) is 2,4-di-TMS. 1118 A is A-1i and (R³)_(n) is 2,6-di-TMS. 1119A is A-1i and (R³)_(n) is 2-Cl-6-F. 1120 A is A-1i and (R³)_(n) is2-Cl-4-F. 1121 A is A-1j and (R³)_(n) is H. 1122 A is A-1j and (R³)_(n)is 2-F. 1123 A is A-1j and (R³)_(n) is 2,4-di-F. 1124 A is A-1j and(R³)_(n) is 2,6-di-F. 1125 A is A-1j and (R³)_(n) is 2-Cl. 1126 A isA-1j and (R³)_(n) is 2,4-di-Cl. 1127 A is A-1j and (R³)_(n) is2,6-di-Cl. 1128 A is A-1j and (R³)_(n) is 2-Br. 1129 A is A-1j and(R³)_(n) is 2,4-di-Br. 1130 A is A-1j and (R³)_(n) is 2,6-di-Br. 1131 Ais A-1j and (R³)_(n) is 2-I. 1132 A is A-1j and (R³)_(n) is 2,4-di-I.1133 A is A-1j and (R³)_(n) is 2,6-di-I. 1134 A is A-1j and (R³)_(n) is2-Me. 1135 A is A-1j and (R³)_(n) is 2,4-di-Me. 1136 A is A-1j and(R³)_(n) is 2,6-di-Me. 1137 A is A-1j and (R³)_(n) is 2-Et. 1138 A isA-1j and (R³)_(n) is 2,4-di-Et. 1139 A is A-1j and (R³)_(n) is2,6-di-Et. 1140 A is A-1j and (R³)_(n) is 2-i-Pr. 1141 A is A-1j and(R³)_(n) is 2,4-di-i-Pr. 1142 A is A-1j and (R³)_(n) is 2,6-di-i-Pr.1143 A is A-1j and (R³)_(n) is 2-c-Pr. 1144 A is A-1j and (R³)_(n) is2,4-di-c-Pr. 1145 A is A-1j and (R³)_(n) is 2,6-di-c-Pr. 1146 A is A-1jand (R³)_(n) is 2-CF₃. 1147 A is A-1j and (R³)_(n) is 2,4-di-CF₃. 1148 Ais A-1j and (R³)_(n) is 2,6-di-CF₃. 1149 A is A-1j and (R³)_(n) is2-OMe. 1150 A is A-1j and (R³)_(n) is 2,4-di-OMe. 1151 A is A-1j and(R³)_(n) is 2,6-di-OMe. 1152 A is A-1j and (R³)_(n) is 2-OCF₃. 1153 A isA-1j and (R³)_(n) is 2,4-di-OCF₃. 1154 A is A-1j and (R³)_(n) is2,6-di-OCF₃. 1155 A is A-1j and (R³)_(n) is 2-TMS. 1156 A is A-1j and(R³)_(n) is 2,4-di-TMS. 1157 A is A-1j and (R³)_(n) is 2,6-di-TMS. 1158A is A-1j and (R³)_(n) is 2-Cl-6-F. 1159 A is A-1j and (R³)_(n) is2-Cl-4-F. 1160 A is A-1a and (R³)_(n) is 4-F. 1161 A is A-1a and(R³)_(n) is 2,5-di-F. 1162 A is A-1a and (R³)_(n) is 4,5-di-F. 1163 A isA-1a and (R³)_(n) is 4-Cl. 1164 A is A-1a and (R³)_(n) is 2,5-di-Cl.1165 A is A-1a and (R³)_(n) is 4,5-di-Cl. 1166 A is A-1a and (R³)_(n) is4-Br. 1167 A is A-1a and (R³)_(n) is 2,5-di-Br. 1168 A is A-1a and(R³)_(n) is 4,5-di-Br. 1169 A is A-1a and (R³)_(n) is 4-I. 1170 A isA-1a and (R³)_(n) is 2,5-di-I. 1171 A is A-1a and (R³)_(n) is 4,5-di-I.1172 A is A-1a and (R³)_(n) is 4-Me. 1173 A is A-1a and (R³)_(n) is2,5-di-Me. 1174 A is A-1a and (R³)_(n) is 4,5-di-Me. 1175 A is A-1a and(R³)_(n) is 4-Et. 1176 A is A-1a and (R³)_(n) is 2,5-di-Et. 1177 A isA-1a and (R³)_(n) is 4,5-di-Et. 1178 A is A-1a and (R³)_(n) is 4-i-Pr.1179 A is A-1a and (R³)_(n) is 2,5-di-i-Pr. 1180 A is A-1a and (R³)_(n)is 4,5-di-i-Pr. 1181 A is A-1a and (R³)_(n) is 4-c-Pr. 1182 A is A-1aand (R³)_(n) is 2,5-di-c-Pr. 1183 A is A-1a and (R³)_(n) is 4,5-di-c-Pr.1184 A is A-1a and (R³)_(n) is 4-CF₃. 1185 A is A-1a and (R³)_(n) is2,5-di-CF₃. 1186 A is A-1a and (R³)_(n) is 4,5-di-CF₃. 1187 A is A-1aand (R³)_(n) is 4-OMe. 1188 A is A-1a and (R³)_(n) is 2,5-di-OMe. 1189 Ais A-1a and (R³)_(n) is 4,5-di-OMe. 1190 A is A-1a and (R³)_(n) is4-CF₃O. 1191 A is A-1a and (R³)_(n) is 2,5-di-OCF₃. 1192 A is A-1a and(R³)_(n) is 4,5-di-OCF₃. 1193 A is A-1a and (R³)_(n) is 4-TMS. 1194 A isA-1a and (R³)_(n) is 2,5-di-TMS. 1195 A is A-1a and (R³)_(n) is4,5-di-TMS. 1196 A is A-1a and (R³)_(n) is 2-Cl-6-Me. 1197 A is A-1a and(R³)_(n) is 2-Cl-4-Me. 1198 A is A-1b and (R³)_(n) is 4-F. 1199 A isA-1b and (R³)_(n) is 2,5-di-F. 1200 A is A-1b and (R³)_(n) is 4,5-di-F.1201 A is A-1b and (R³)_(n) is 4-Cl. 1202 A is A-1b and (R³)_(n) is2,5-di-Cl. 1203 A is A-1b and (R³)_(n) is 4,5-di-Cl. 1204 A is A-1b and(R³)_(n) is 4-Br. 1205 A is A-1b and (R³)_(n) is 2,5-di-Br. 1206 A isA-1b and (R³)_(n) is 4,5-di-Br. 1207 A is A-1b and (R³)_(n) is 4-I. 1208A is A-1b and (R³)_(n) is 2,5-di-I. 1209 A is A-1b and (R³)_(n) is4,5-di-I. 1210 A is A-1b and (R³)_(n) is 4-Me. 1211 A is A-1b and(R³)_(n) is 2,5-di-Me. 1212 A is A-1b and (R³)_(n) is 4,5-di-Me. 1213 Ais A-1b and (R³)_(n) is 4-Et. 1214 A is A-1b and (R³)_(n) is 2,5-di-Et.1215 A is A-1b and (R³)_(n) is 4,5-di-Et. 1216 A is A-1b and (R³)_(n) is4-i-Pr. 1217 A is A-1b and (R³)_(n) is 2,5-di-i-Pr. 1218 A is A-1b and(R³)_(n) is 4,5-di-i-Pr. 1219 A is A-1b and (R³)_(n) is 4-c-Pr. 1220 Ais A-1b and (R³)_(n) is 2,5-di-c-Pr. 1221 A is A-1b and (R³)_(n) is4,5-di-c-Pr. 1222 A is A-1b and (R³)_(n) is 4-CF₃. 1223 A is A-1b and(R³)_(n) is 2,5-di-CF₃. 1224 A is A-1b and (R³)_(n) is 4,5-di-CF₃. 1225A is A-1b and (R³)_(n) is 4-OMe. 1226 A is A-1b and (R³)_(n) is2,5-di-OMe. 1227 A is A-1b and (R³)_(n) is 4,5-di-OMe. 1228 A is A-1band (R³)_(n) is 4-OCF₃. 1229 A is A-1b and (R³)_(n) is 2,5-di-OCF₃. 1230A is A-1b and (R³)_(n) is 4,5-di-OCF₃. 1231 A is A-1b and (R³)_(n) is4-TMS. 1232 A is A-1b and (R³)_(n) is 2,5-di-TMS. 1233 A is A-1b and(R³)_(n) is 4,5-di-TMS. 1234 A is A-1b and (R³)_(n) is 2-Cl-6-Me. 1235 Ais A-1b and (R³)_(n) is 2-Cl-4-Me. 1236 A is A-1c and (R³)_(n) is 4-F.1237 A is A-1c and (R³)_(n) is 2,5-di-F. 1238 A is A-1c and (R³)_(n) is4,5-di-F. 1239 A is A-1c and (R³)_(n) is 4-Cl. 1240 A is A-1c and(R³)_(n) is 2,5-di-Cl. 1241 A is A-1c and (R³)_(n) is 4,5-di-Cl. 1242 Ais A-1c and (R³)_(n) is 4-Br. 1243 A is A-1c and (R³)_(n) is 2,5-di-Br.1244 A is A-1c and (R³)_(n) is 4,5-di-Br. 1245 A is A-1c and (R³)_(n) is4-I. 1246 A is A-1c and (R³)_(n) is 2,5-di-I. 1247 A is A-1c and(R³)_(n) is 4,5-di-I. 1248 A is A-1c and (R³)_(n) is 4-Me. 1249 A isA-1c and (R³)_(n) is 2,5-di-Me. 1250 A is A-1c and (R³)_(n) is4,5-di-Me. 1251 A is A-1c and (R³)_(n) is 4-Et. 1252 A is A-1c and(R³)_(n) is 2,5-di-Et. 1253 A is A-1c and (R³)_(n) is 4,5-di-Et. 1254 Ais A-1c and (R³)_(n) is 4-i-Pr. 1255 A is A-1c and (R³)_(n) is2,5-di-i-Pr. 1256 A is A-1c and (R³)_(n) is 4,5-di-i-Pr. 1257 A is A-1cand (R³)_(n) is 4-c-Pr. 1258 A is A-1c and (R³)_(n) is 2,5-di-c-Pr. 1259A is A-1c and (R³)_(n) is 4,5-di-c-Pr. 1260 A is A-1c and (R³)_(n) is4-CF₃. 1261 A is A-1c and (R³)_(n) is 2,5-di-CF₃. 1262 A is A-1c and(R³)_(n) is 4,5-di-CF₃. 1263 A is A-1c and (R³)_(n) is 4-OMe. 1264 A isA-1c and (R³)_(n) is 2,5-di-OMe. 1265 A is A-1c and (R³)_(n) is4,5-di-OMe. 1266 A is A-1c and (R³)_(n) is 4-OCF₃. 1267 A is A-1c and(R³)_(n) is 2,5-di-OCF₃. 1268 A is A-1c and (R³)_(n) is 4,5-di-OCF₃.1269 A is A-1c and (R³)_(n) is 4-TMS. 1270 A is A-1c and (R³)_(n) is2,5-di-TMS. 1271 A is A-1c and (R³)_(n) is 4,5-di-TMS. 1272 A is A-1cand (R³)_(n) is 2-Cl-6-Me. 1273 A is A-1c and (R³)_(n) is 2-Cl-4-Me.1274 A is A-1d and (R³)_(n) is 4-F. 1275 A is A-1d and (R³)_(n) is2,5-di-F. 1276 A is A-1d and (R³)_(n) is 4,5-di-F. 1277 A is A-1d and(R³)_(n) is 4-Cl. 1278 A is A-1d and (R³)_(n) is 2,5-di-Cl. 1279 A isA-1d and (R³)_(n) is 4,5-di-Cl. 1280 A is A-1d and (R³)_(n) is 4-Br.1281 A is A-1d and (R³)_(n) is 2,5-di-Br. 1282 A is A-1d and (R³)_(n) is4,5-di-Br. 1283 A is A-1d and (R³)_(n) is 4-I. 1284 A is A-1d and(R³)_(n) is 2,5-di-I. 1285 A is A-1d and (R³)_(n) is 4,5-di-I. 1286 A isA-1d and (R³)_(n) is 4-Me. 1287 A is A-1d and (R³)_(n) is 2,5-di-Me.1288 A is A-1d and (R³)_(n) is 4,5-di-Me. 1289 A is A-1d and (R³)_(n) is4-Et. 1290 A is A-1d and (R³)_(n) is 2,5-di-Et. 1291 A is A-1d and(R³)_(n) is 4,5-di-Et. 1292 A is A-1d and (R³)_(n) is 4-i-Pr. 1293 A isA-1d and (R³)_(n) is 2,5-di-i-Pr. 1294 A is A-1d and (R³)_(n) is4,5-di-i-Pr. 1295 A is A-1d and (R³)_(n) is 4-c-Pr. 1296 A is A-1d and(R³)_(n) is 2,5-di-c-Pr. 1297 A is A-1d and (R³)_(n) is 4,5-di-c-Pr.1298 A is A-1d and (R³)_(n) is 4-CF₃. 1299 A is A-1d and (R³)_(n) is2,5-di-CF₃. 1300 A is A-1d and (R³)_(n) is 4,5-di-CF₃. 1301 A is A-1dand (R³)_(n) is 4-OMe. 1302 A is A-1d and (R³)_(n) is 2,5-di-OMe. 1303 Ais A-1d and (R³)_(n) is 4,5-di-OMe. 1304 A is A-1d and (R³)_(n) is4-OCF₃. 1305 A is A-1d and (R³)_(n) is 2,5-di-OCF₃. 1306 A is A-1d and(R³)_(n) is 4,5-di-OCF₃. 1307 A is A-1d and (R³)_(n) is 4-TMS. 1308 A isA-1d and (R³)_(n) is 2,5-di-TMS. 1309 A is A-1d and (R³)_(n) is4,5-di-TMS. 1310 A is A-1d and (R³)_(n) is 2-Cl-6-Me. 1311 A is A-1d and(R³)_(n) is 2-Cl-4-Me. 1312 A is A-1e and (R³)_(n) is 4-F. 1313 A isA-1e and (R³)_(n) is 2,5-di-F. 1314 A is A-1e and (R³)_(n) is 4,5-di-F.1315 A is A-1e and (R³)_(n) is 4-Cl. 1316 A is A-1e and (R³)_(n) is2,5-di-Cl. 1317 A is A-1e and (R³)_(n) is 4,5-di-Cl. 1318 A is A-1e and(R³)_(n) is 4-Br. 1319 A is A-1e and (R³)_(n) is 2,5-di-Br. 1320 A isA-1e and (R³)_(n) is 4,5-di-Br. 1321 A is A-1e and (R³)_(n) is 4-I. 1322A is A-1e and (R³)_(n) is 2,5-di-I. 1323 A is A-1e and (R³)_(n) is4,5-di-I. 1324 A is A-1e and (R³)_(n) is 4-Me. 1325 A is A-1e and(R³)_(n) is 2,5-di-Me. 1326 A is A-1e and (R³)_(n) is 4,5-di-Me. 1327 Ais A-1e and (R³)_(n) is 4-Et. 1328 A is A-1e and (R³)_(n) is 2,5-di-Et.1329 A is A-1e and (R³)_(n) is 4,5-di-Et. 1330 A is A-1e and (R³)_(n) is4-i-Pr. 1331 A is A-1e and (R³)_(n) is 2,5-di-i-Pr. 1332 A is A-1e and(R³)_(n) is 4,5-di-i-Pr. 1333 A is A-1e and (R³)_(n) is 4-c-Pr. 1334 Ais A-1e and (R³)_(n) is 2,5-di-c-Pr. 1335 A is A-1e and (R³)_(n) is4,5-di-c-Pr. 1336 A is A-1e and (R³)_(n) is 4-CF₃. 1337 A is A-1e and(R³)_(n) is 2,5-di-CF₃. 1338 A is A-1e and (R³)_(n) is 4,5-di-CF₃. 1339A is A-1e and (R³)_(n) is 4-OMe. 1340 A is A-1e and (R³)_(n) is2,5-di-OMe. 1341 A is A-1e and (R³)_(n) is 4,5-di-OMe. 1342 A is A-1eand (R³)_(n) is 4-OCF₃. 1343 A is A-1e and (R³)_(n) is 2,5-di-OCF₃. 1344A is A-1e and (R³)_(n) is 4,5-di-OCF₃. 1345 A is A-1e and (R³)_(n) is4-TMS. 1346 A is A-1e and (R³)_(n) is 2,5-di-TMS. 1347 A is A-1e and(R³)_(n) is 4,5-di-TMS. 1348 A is A-1e and (R³)_(n) is 2-Cl-6-Me. 1349 Ais A-1e and (R³)_(n) is 2-Cl-4-Me. 1350 A is A-1f and (R³)_(n) is 4-F.1351 A is A-1f and (R³)_(n) is 2,5-di-F. 1352 A is A-1f and (R³)_(n) is4,5-di-F. 1353 A is A-1f and (R³)_(n) is 4-Cl. 1354 A is A-1f and(R³)_(n) is 2,5-di-Cl. 1355 A is A-1f and (R³)_(n) is 4,5-di-Cl. 1356 Ais A-1f and (R³)_(n) is 4-Br. 1357 A is A-1f and (R³)_(n) is 2,5-di-Br.1358 A is A-1f and (R³)_(n) is 4,5-di-Br. 1359 A is A-1f and (R³)_(n) is4-I. 1360 A is A-1f and (R³)_(n) is 2,5-di-I. 1361 A is A-1f and(R³)_(n) is 4,5-di-I. 1362 A is A-1f and (R³)_(n) is 4-Me. 1363 A isA-1f and (R³)_(n) is 2,5-di-Me. 1364 A is A-1f and (R³)_(n) is4,5-di-Me. 1365 A is A-1f and (R³)_(n) is 4-Et. 1366 A is A-1f and(R³)_(n) is 2,5-di-Et. 1367 A is A-1f and (R³)_(n) is 4,5-di-Et. 1368 Ais A-1f and (R³)_(n) is 4-i-Pr. 1369 A is A-1f and (R³)_(n) is2,5-di-i-Pr. 1370 A is A-1f and (R³)_(n) is 4,5-di-i-Pr. 1371 A is A-1fand (R³)_(n) is 4-c-Pr. 1372 A is A-1f and (R³)_(n) is 2,5-di-c-Pr. 1373A is A-1f and (R³)_(n) is 4,5-di-c-Pr. 1374 A is A-1f and (R³)_(n) is4-CF₃. 1375 A is A-1f and (R³)_(n) is 2,5-di-CF₃. 1376 A is A-1f and(R³)_(n) is 4,5-di-CF₃. 1377 A is A-1f and (R³)_(n) is 4-OMe. 1378 A isA-1f and (R³)_(n) is 2,5-di-OMe. 1379 A is A-1f and (R³)_(n) is4,5-di-OMe. 1380 A is A-1f and (R³)_(n) is 4-OCF₃. 1381 A is A-1f and(R³)_(n) is 2,5-di-OCF₃. 1382 A is A-1f and (R³)_(n) is 4,5-di-OCF₃.1383 A is A-1f and (R³)_(n) is 4-TMS. 1384 A is A-1f and (R³)_(n) is2,5-di-TMS. 1385 A is A-1f and (R³)_(n) is 4,5-di-TMS. 1386 A is A-1fand (R³)_(n) is 2-Cl-6-Me. 1387 A is A-1f and (R³)_(n) is 2-Cl-4-Me.1388 A is A-1g and (R³)_(n) is 4-F. 1389 A is A-1g and (R³)_(n) is2,5-di-F. 1390 A is A-1g and (R³)_(n) is 4,5-di-F. 1391 A is A-1g and(R³)_(n) is 4-Cl. 1392 A is A-1g and (R³)_(n) is 2,5-di-Cl. 1393 A isA-1g and (R³)_(n) is 4,5-di-Cl. 1394 A is A-1g and (R³)_(n) is 4-Br.1395 A is A-1g and (R³)_(n) is 2,5-di-Br. 1396 A is A-1g and (R³)_(n) is4,5-di-Br. 1397 A is A-1g and (R³)_(n) is 4-I. 1398 A is A-1g and(R³)_(n) is 2,5-di-I. 1399 A is A-1g and (R³)_(n) is 4,5-di-I. 1400 A isA-1g and (R³)_(n) is 4-Me. 1401 A is A-1g and (R³)_(n) is 2,5-di-Me.1402 A is A-1g and (R³)_(n) is 4,5-di-Me. 1403 A is A-1g and (R³)_(n) is4-Et. 1404 A is A-1g and (R³)_(n) is 2,5-di-Et. 1405 A is A-1g and(R³)_(n) is 4,5-di-Et. 1406 A is A-1g and (R³)_(n) is 4-i-Pr. 1407 A isA-1g and (R³)_(n) is 2,5-di-i-Pr. 1408 A is A-1g and (R³)_(n) is4,5-di-i-Pr. 1409 A is A-1g and (R³)_(n) is 4-c-Pr. 1410 A is A-1g and(R³)_(n) is 2,5-di-c-Pr. 1411 A is A-1g and (R³)_(n) is 4,5-di-c-Pr.1412 A is A-1g and (R³)_(n) is 4-CF₃. 1413 A is A-1g and (R³)_(n) is2,5-di-CF₃. 1414 A is A-1g and (R³)_(n) is 4,5-di-CF₃. 1415 A is A-1gand (R³)_(n) is 4-OMe. 1416 A is A-1g and (R³)_(n) is 2,5-di-OMe. 1417 Ais A-1g and (R³)_(n) is 4,5-di-OMe. 1418 A is A-1g and (R³)_(n) is4-OCF₃. 1419 A is A-1g and (R³)_(n) is 2,5-di-OCF₃. 1420 A is A-1g and(R³)_(n) is 4,5-di-OCF₃. 1421 A is A-1g and (R³)_(n) is 4-TMS. 1422 A isA-1g and (R³)_(n) is 2,5-di-TMS. 1423 A is A-1g and (R³)_(n) is4,5-di-TMS. 1424 A is A-1g and (R³)_(n) is 2-Cl-6-Me. 1425 A is A-1g and(R³)_(n) is 2-Ci-4-Me. 1426 A is A-1h and (R³)_(n) is 4-F. 1427 A isA-1h and (R³)_(n) is 2,5-di-F. 1428 A is A-1h and (R³)_(n) is 4,5-di-F.1429 A is A-1h and (R³)_(n) is 4-Cl. 1430 A is A-1h and (R³)_(n) is2,5-di-Cl. 1431 A is A-1h and (R³)_(n) is 4,5-di-Cl. 1432 A is A-1h and(R³)_(n) is 4-Br. 1433 A is A-1h and (R³)_(n) is 2,5-di-Br. 1434 A isA-1h and (R³)_(n) is 4,5-di-Br. 1435 A is A-1h and (R³)_(n) is 4-I. 1436A is A-1h and (R³)_(n) is 2,5-di-I. 1437 A is A-1h and (R³)_(n) is4,5-di-I. 1438 A is A-1h and (R³)_(n) is 4-Me. 1439 A is A-1h and(R³)_(n) is 2,5-di-Me. 1440 A is A-1h and (R³)_(n) is 4,5-di-Me. 1441 Ais A-1h and (R³)_(n) is 4-Et. 1442 A is A-1h and (R³)_(n) is 2,5-di-Et.1443 A is A-1h and (R³)_(n) is 4,5-di-Et. 1444 A is A-1h and (R³)_(n) is4-i-Pr. 1445 A is A-1h and (R³)_(n) is 2,5-di-i-Pr. 1446 A is A-1h and(R³)_(n) is 4,5-di-i-Pr. 1447 A is A-1h and (R³)_(n) is 4-c-Pr. 1448 Ais A-1h and (R³)_(n) is 2,5-di-c-Pr. 1449 A is A-1h and (R³)_(n) is4,5-di-c-Pr. 1450 A is A-1h and (R³)_(n) is 4-CF₃. 1451 A is A-1h and(R³)_(n) is 2,5-di-CF₃. 1452 A is A-1h and (R³)_(n) is 4,5-di-CF₃. 1453A is A-1h and (R³)_(n) is 4-OMe. 1454 A is A-1h and (R³)_(n) is2,5-di-OMe. 1455 A is A-1h and (R³)_(n) is 4,5-di-OMe. 1456 A is A-1hand (R³)_(n) is 4-OCF₃. 1457 A is A-1h and (R³)_(n) is 2,5-di-OCF₃ 1458A is A-1h and (R³)_(n) is 4,5-di-OCF₃. 1459 A is A-1h and (R³)_(n) is4-TMS. 1460 A is A-1h and (R³)_(n) is 2,5-di-TMS. 1461 A is A-1h and(R³)_(n) is 4,5-di-TMS. 1462 A is A-1h and (R³)_(n) is 2-Cl-6-Me. 1463 Ais A-1h and (R³)_(n) is 2-Cl-4-Me. 1464 A is A-1i and (R³)_(n) is 4-F.1465 A is A-1i and (R³)_(n) is 2,5-di-F. 1466 A is A-1i and (R³)_(n) is4,5-di-F. 1467 A is A-1i and (R³)_(n) is 4-Cl. 1468 A is A-1i and(R³)_(n) is 2,5-di-Cl. 1469 A is A-1i and (R³)_(n) is 4,5-di-Cl. 1470 Ais A-1i and (R³)_(n) is 4-Br. 1471 A is A-1i and (R³)_(n) is 2,5-di-Br.1472 A is A-1i and (R³)_(n) is 4,5-di-Br. 1473 A is A-1i and (R³)_(n) is4-I. 1474 A is A-1i and (R³)_(n) is 2,5-di-I. 1475 A is A-1i and(R³)_(n) is 4,5-di-I. 1476 A is A-1i and (R³)_(n) is 4-Me. 1477 A isA-1i and (R³)_(n) is 2,5-di-Me. 1478 A is A-1i and (R³)_(n) is4,5-di-Me. 1479 A is A-1i and (R³)_(n) is 4-Et. 1480 A is A-1i and(R³)_(n) is 2,5-di-Et. 1481 A is A-1i and (R³)_(n) is 4,5-di-Et. 1482 Ais A-1i and (R³)_(n) is 4-i-Pr. 1483 A is A-1i and (R³)_(n) is2,5-di-i-Pr. 1484 A is A-1i and (R³)_(n) is 4,5-di-i-Pr. 1485 A is A-1iand (R³)_(n) is 4-c-Pr. 1486 A is A-1i and (R³)_(n) is 2,5-di-c-Pr. 1487A is A-1i and (R³)_(n) is 4,5-di-c-Pr. 1488 A is A-1i and (R³)_(n) is4-CF₃. 1489 A is A-1i and (R³)_(n) is 2,5-di-CF₃. 1490 A is A-1i and(R³)_(n) is 4,5-di-CF₃. 1491 A is A-1i and (R³)_(n) is 4-OMe. 1492 A isA-1i and (R³)_(n) is 2,5-di-OMe. 1493 A is A-1i and (R³)_(n) is4,5-di-OMe. 1494 A is A-1i and (R³)_(n) is 4-OCF₃. 1495 A is A-1i and(R³)_(n) is 2,5-di-OCF₃. 1496 A is A-1i and (R³)_(n) is 4,5-di-OCF₃.1497 A is A-1i and (R³)_(n) is 4-TMS. 1498 A is A-1i and (R³)_(n) is2,5-di-TMS. 1499 A is A-1i and (R³)_(n) is 4,5-di-TMS. 1500 A is A-1iand (R³)_(n) is 2-Cl-6-Me. 1501 A is A-1i and (R³)_(n) is 2-Cl-4-Me.1502 A is A-1j and (R³)_(n) is 4-F. 1503 A is A-1j and (R³)_(n) is2,5-di-F. 1504 A is A-1j and (R³)_(n) is 4,5-di-F. 1505 A is A-1j and(R³)_(n) is 4-Cl. 1506 A is A-1j and (R³)_(n) is 2,5-di-Cl. 1507 A isA-1j and (R³)_(n) is 4,5-di-Cl. 1508 A is A-1j and (R³)_(n) is 4-Br.1509 A is A-1j and (R³)_(n) is 2,5-di-Br. 1510 A is A-1j and (R³)_(n) is4,5-di-Br. 1511 A is A-1j and (R³)_(n) is 4-I. 1512 A is A-1j and(R³)_(n) is 2,5-di-I. 1513 A is A-1j and (R³)_(n) is 4,5-di-I. 1514 A isA-1j and (R³)_(n) is 4-Me. 1515 A is A-1j and (R³)_(n) is 2,5-di-Me.1516 A is A-1j and (R³)_(n) is 4,5-di-Me. 1517 A is A-1j and (R³)_(n) is4-Et. 1518 A is A-1j and (R³)_(n) is 2,5-di-Et. 1519 A is A-1j and(R³)_(n) is 4,5-di-Et. 1520 A is A-1j and (R³)_(n) is 4-i-Pr. 1521 A isA-1j and (R³)_(n) is 2,5-di-i-Pr. 1522 A is A-1j and (R³)_(n) is4,5-di-i-Pr. 1523 A is A-1j and (R³)_(n) is 4-c-Pr. 1524 A is A-1j and(R³)_(n) is 2,5-di-c-Pr. 1525 A is A-1j and (R³)_(n) is 4,5-di-c-Pr.1526 A is A-1j and (R³)_(n) is 4-CF₃. 1527 A is A-1j and (R³)_(n) is2,5-di-CF₃. 1528 A is A-1j and (R³)_(n) is 4,5-di-CF₃. 1529 A is A-1jand (R³)_(n) is 4-OMe. 1530 A is A-1j and (R³)_(n) is 2,5-di-OMe. 1531 Ais A-1j and (R³)_(n) is 4,5-di-OMe. 1532 A is A-1j and (R³)_(n) is4-OCF₃. 1533 A is A-1j and (R³)_(n) is 2,5-di-OCF₃. 1534 A is A-1j and(R³)_(n) is 4,5-di-OCF₃. 1535 A is A-1j and (R³)_(n) is 4-TMS. 1536 A isA-1j and (R³)_(n) is 2,5-di-TMS. 1537 A is A-1j and (R³)_(n) is4,5-di-TMS. 1538 A is A-1j and (R³)_(n) is 2-Cl-6-Me. 1539 A is A-1j and(R³)_(n) is 2-Cl-4-Me.

Formulation/Utility

A compound of Formula 1 of this invention (including N-oxides and saltsthereof) will generally be used as a fungicidal active ingredient in acomposition, i.e. formulation, with at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents, which serve as a carrier. The formulation orcomposition ingredients are selected to be consistent with the physicalproperties of the active ingredient, mode of application andenvironmental factors such as soil type, moisture and temperature.

Useful formulations include both liquid and solid compositions. Liquidcompositions include solutions (including emulsifiable concentrates),suspensions, emulsions (including microemulsions, oil-in-wateremulsions, flowable concentrates and/or suspoemulsions) and the like,which optionally can be thickened into gels. The general types ofaqueous liquid compositions are soluble concentrate, suspensionconcentrate, capsule suspension, concentrated emulsion, microemulsion,oil-in-water emulsion, flowable concentrate and suspo-emulsion. Thegeneral types of nonaqueous liquid compositions are emulsifiableconcentrate, microemulsifiable concentrate, dispersible concentrate andoil dispersion.

The general types of solid compositions are dusts, powders, granules,pellets, prills, pastilles, tablets, filled films (including seedcoatings) and the like, which can be water-dispersible (“wettable”) orwater-soluble. Films and coatings formed from film-forming solutions orflowable suspensions are particularly useful for seed treatment. Activeingredient can be (micro)encapsulated and further formed into asuspension or solid formulation; alternatively the entire formulation ofactive ingredient can be encapsulated (or “overcoated”). Encapsulationcan control or delay release of the active ingredient. An emulsifiablegranule combines the advantages of both an emulsifiable concentrateformulation and a dry granular formulation. High-strength compositionsare primarily used as intermediates for further formulation.

Sprayable formulations are typically extended in a suitable mediumbefore spraying. Such liquid and solid formulations are formulated to bereadily diluted in the spray medium, usually water, but occasionallyanother suitable medium like an aromatic or paraffinic hydrocarbon orvegetable oil. Spray volumes can range from about one to severalthousand liters per hectare, but more typically are in the range fromabout ten to several hundred liters per hectare. Sprayable formulationscan be tank mixed with water or another suitable medium for foliartreatment by aerial or ground application, or for application to thegrowing medium of the plant. Liquid and dry formulations can be metereddirectly into drip irrigation systems or metered into the furrow duringplanting. Liquid and solid formulations can be applied onto seeds ofcrops and other desirable vegetation as seed treatments before plantingto protect developing roots and other subterranean plant parts and/orfoliage through systemic uptake.

The formulations will typically contain effective amounts of activeingredient, diluent and surfactant within the following approximateranges which add up to 100 percent by weight.

Weight Percent Active Ingredient Diluent Surfactant Water-Dispersibleand Water-soluble 0.001- 0-  0-15 Granules, Tablets and Powders 9099.999 Oil Dispersions, Suspensions,  1-50 40-99  0-50 Emulsions,Solutions (including Emulsifiable Concentrates) Dusts  1-25 70-99 0-5Granules and Pellets 0.001- 5-  0-15 95 99.999 High StrengthCompositions 90-99  0-10 0-2

Solid diluents include, for example, clays such as bentonite,montmorillonite, attapulgite and kaolin, gypsum, cellulose, titaniumdioxide, zinc oxide, starch, dextrin, sugars (e.g., lactose, sucrose),silica, talc, mica, diatomaceous earth, urea, calcium carbonate, sodiumcarbonate and bicarbonate, and sodium sulfate. Typical solid diluentsare described in Watkins et al., Handbook of Insecticide Dust Diluentsand Carriers, 2nd Ed., Dorland Books, Caldwell, N.J.

Liquid diluents include, for example, water, N,N-dimethylalkanamides(e.g., N,N-dimethylformamide), limonene, dimethyl sulfoxide,N-alkylpyrrolidones (e.g., N-methylpyrrolidinone), alkyl phosphates(e.g., triethyl phosphate), ethylene glycol, triethylene glycol,propylene glycol, dipropylene glycol, polypropylene glycol, propylenecarbonate, butylene carbonate, paraffins (e.g., white mineral oils,normal paraffins, isoparaffins), alkylbenzenes, alkylnaphthalenes,glycerine, glycerol triacetate, sorbitol, aromatic hydrocarbons,dearomatized aliphatics, alkylbenzenes, alkylnaphthalenes, ketones suchas cyclohexanone, 2-heptanone, isophorone and4-hydroxy-4-methyl-2-pentanone, acetates such as isoamyl acetate, hexylacetate, heptyl acetate, octyl acetate, nonyl acetate, tridecyl acetateand isobornyl acetate, other esters such as alkylated lactate esters,dibasic esters, alkyl and aryl benzoates and γ-butyrolactone, andalcohols, which can be linear, branched, saturated or unsaturated, suchas methanol, ethanol, n-propanol, isopropyl alcohol, n-butanol, isobutylalcohol, n-hexanol, 2-ethylhexanol, n-octanol, decanol, isodecylalcohol, isooctadecanol, cetyl alcohol, lauryl alcohol, tridecylalcohol, oleyl alcohol, cyclohexanol, tetrahydrofurfuryl alcohol,diacetone alcohol, cresol and benzyl alcohol. Liquid diluents alsoinclude glycerol esters of saturated and unsaturated fatty acids(typically C₆-C₂₂), such as plant seed and fruit oils (e.g., oils ofolive, castor, linseed, sesame, corn (maize), peanut, sunflower,grapeseed, safflower, cottonseed, soybean, rapeseed, coconut and palmkernel), animal-sourced fats (e.g., beef tallow, pork tallow, lard, codliver oil, fish oil), and mixtures thereof. Liquid diluents also includealkylated fatty acids (e.g., methylated, ethylated, butylated) whereinthe fatty acids may be obtained by hydrolysis of glycerol esters fromplant and animal sources, and can be purified by distillation. Typicalliquid diluents are described in Marsden, Solvents Guide, 2nd Ed.,Interscience, New York, 1950.

The solid and liquid compositions of the present invention often includeone or more surfactants. When added to a liquid, surfactants (also knownas “surface-active agents”) generally modify, most often reduce, thesurface tension of the liquid. Depending on the nature of thehydrophilic and lipophilic groups in a surfactant molecule, surfactantscan be useful as wetting agents, dispersants, emulsifiers or defoamingagents.

Surfactants can be classified as nonionic, anionic or cationic. Nonionicsurfactants useful for the present compositions include, but are notlimited to: alcohol alkoxylates such as alcohol alkoxylates based onnatural and synthetic alcohols (which may be branched or linear) andprepared from the alcohols and ethylene oxide, propylene oxide, butyleneoxide or mixtures thereof; amine ethoxylates, alkanolamides andethoxylated alkanolamides; alkoxylated triglycerides such as ethoxylatedsoybean, castor and rapeseed oils; alkylphenol alkoxylates such asoctylphenol ethoxylates, nonylphenol ethoxylates, dinonyl phenolethoxylates and dodecyl phenol ethoxylates (prepared from the phenolsand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); block polymers prepared from ethylene oxide or propylene oxideand reverse block polymers where the terminal blocks are prepared frompropylene oxide; ethoxylated fatty acids; ethoxylated fatty esters andoils; ethoxylated methyl esters; ethoxylated tristyrylphenol (includingthose prepared from ethylene oxide, propylene oxide, butylene oxide ormixtures thereof); fatty acid esters, glycerol esters, lanolin-basedderivatives, polyethoxylate esters such as polyethoxylated sorbitanfatty acid esters, polyethoxylated sorbitol fatty acid esters andpolyethoxylated glycerol fatty acid esters; other sorbitan derivativessuch as sorbitan esters; polymeric surfactants such as randomcopolymers, block copolymers, alkyd peg (polyethylene glycol) resins,graft or comb polymers and star polymers; polyethylene glycols (pegs);polyethylene glycol fatty acid esters; silicone-based surfactants; andsugar-derivatives such as sucrose esters, alkyl polyglycosides and alkylpolysaccharides.

Useful anionic surfactants include, but are not limited to: alkylarylsulfonic acids and their salts; carboxylated alcohol or alkylphenolethoxylates; diphenyl sulfonate derivatives; lignin and ligninderivatives such as lignosulfonates; maleic or succinic acids or theiranhydrides; olefin sulfonates; phosphate esters such as phosphate estersof alcohol alkoxylates, phosphate esters of alkylphenol alkoxylates andphosphate esters of styryl phenol ethoxylates; protein-basedsurfactants; sarcosine derivatives; styryl phenol ether sulfate;sulfates and sulfonates of oils and fatty acids; sulfates and sulfonatesof ethoxylated alkylphenols; sulfates of alcohols; sulfates ofethoxylated alcohols; sulfonates of amines and amides such asN,N-alkyltaurates; sulfonates of benzene, cumene, toluene, xylene, anddodecyl and tridecylbenzenes; sulfonates of condensed naphthalenes;sulfonates of naphthalene and alkyl naphthalene; sulfonates offractionated petroleum; sulfosuccinamates; and sulfosuccinates and theirderivatives such as dialkyl sulfosuccinate salts.

Useful cationic surfactants include, but are not limited to: amides andethoxylated amides; amines such as N-alkyl propanediamines,tripropylenetriamines and dipropylenetetramines, and ethoxylated amines,ethoxylated diamines and propoxylated amines (prepared from the aminesand ethylene oxide, propylene oxide, butylene oxide or mixturesthereof); amine salts such as amine acetates and diamine salts;quaternary ammonium salts such as quaternary salts, ethoxylatedquaternary salts and diquaternary salts; and amine oxides such asalkyldimethylamine oxides and bis-(2-hydroxyethyl)-alkylamine oxides.

Also useful for the present compositions are mixtures of nonionic andanionic surfactants or mixtures of nonionic and cationic surfactants.Nonionic, anionic and cationic surfactants and their recommended usesare disclosed in a variety of published references includingMcCutcheon's Emulsifiers and Detergents, annual American andInternational Editions published by McCutcheon's Division, TheManufacturing Confectioner Publishing Co.; Sisely and Wood, Encyclopediaof Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964; andA. S. Davidson and B. Milwidsky, Synthetic Detergents, Seventh Edition,John Wiley and Sons, New York, 1987.

Compositions of this invention may also contain formulation auxiliariesand additives, known to those skilled in the art as formulation aids(some of which may be considered to also function as solid diluents,liquid diluents or surfactants). Such formulation auxiliaries andadditives may control: pH (buffers), foaming during processing(antifoams such polyorganosiloxanes), sedimentation of activeingredients (suspending agents), viscosity (thixotropic thickeners),in-container microbial growth (antimicrobials), product freezing(antifreezes), color (dyes/pigment dispersions), wash-off (film formersor stickers), evaporation (evaporation retardants), and otherformulation attributes. Film formers include, for example, polyvinylacetates, polyvinyl acetate copolymers, polyvinylpyrrolidone-vinylacetate copolymer, polyvinyl alcohols, polyvinyl alcohol copolymers andwaxes. Examples of formulation auxiliaries and additives include thoselisted in McCutcheon's Volume 2: Functional Materials, annualInternational and North American editions published by McCutcheon'sDivision, The Manufacturing Confectioner Publishing Co.; and PCTPublication WO 03/024222.

The compound of Formula 1 and any other active ingredients are typicallyincorporated into the present compositions by dissolving the activeingredient in a solvent or by grinding in a liquid or dry diluent.Solutions, including emulsifiable concentrates, can be prepared bysimply mixing the ingredients. If the solvent of a liquid compositionintended for use as an emulsifiable concentrate is water-immiscible, anemulsifier is typically added to emulsify the active-containing solventupon dilution with water. Active ingredient slurries, with particlediameters of up to 2,000 μm can be wet milled using media mills toobtain particles with average diameters below 3 μm. Aqueous slurries canbe made into finished suspension concentrates (see, for example, U.S.Pat. No. 3,060,084) or further processed by spray drying to formwater-dispersible granules. Dry formulations usually require dry millingprocesses, which produce average particle diameters in the 2 to 10 μmrange. Dusts and powders can be prepared by blending and usuallygrinding (such as with a hammer mill or fluid-energy mill). Granules andpellets can be prepared by spraying the active material upon preformedgranular carriers or by agglomeration techniques. See Browning,“Agglomeration”, Chemical Engineering, Dec. 4, 1967, pp 147-48, Perry'sChemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963,pages 8-57 and following, and WO 91/13546. Pellets can be prepared asdescribed in U.S. Pat. No. 4,172,714. Water-dispersible andwater-soluble granules can be prepared as taught in U.S. Pat. No.4,144,050, U.S. Pat. No. 3,920,442 and DE 3,246,493. Tablets can beprepared as taught in U.S. Pat. No. 5,180,587, U.S. Pat. No. 5,232,701and U.S. Pat. No. 5,208,030. Films can be prepared as taught in GB2,095,558 and U.S. Pat. No. 3,299,566. One embodiment of the presentinvention relates to a method for controlling fungal pathogens,comprising diluting the fungicidal composition of the present invention(a compound of Formula 1 formulated with surfactants, solid diluents andliquid diluents or a formulated mixture of a compound of Formula 1 andat least one other fungicide) with water, and optionally adding anadjuvant to form a diluted composition, and contacting the fungalpathogen or its environment with an effective amount of said dilutedcomposition.

Although a spray composition formed by diluting with water a sufficientconcentration of the present fungicidal composition can providesufficient efficacy for controlling fungal pathogens, separatelyformulated adjuvant products can also be added to spray tank mixtures.These additional adjuvants are commonly known as “spray adjuvants” or“tank-mix adjuvants”, and include any substance mixed in a spray tank toimprove the performance of a pesticide or alter the physical propertiesof the spray mixture. Adjuvants can be anionic or nonionic surfactants,emulsifying agents, petroleum-based crop oils, crop-derived seed oils,acidifiers, buffers, thickeners or defoaming agents. Adjuvants are usedto enhancing efficacy (e.g., biological availability, adhesion,penetration, uniformity of coverage and durability of protection), orminimizing or eliminating spray application problems associated withincompatibility, foaming, drift, evaporation, volatilization anddegradation. To obtain optimal performance, adjuvants are selected withregard to the properties of the active ingredient, formulation andtarget (e.g., crops, insect pests).

The amount of adjuvants added to spray mixtures is generally in therange of about 2.5% to 0.1% by volume. The application rates ofadjuvants added to spray mixtures are typically between about 1 to 5 Lper hectare. Representative examples of spray adjuvants include: Adigor®(Syngenta) 47% methylated rapeseed oil in liquid hydrocarbons, Silwet®(Helena Chemical Company) polyalkyleneoxide modifiedheptamethyltrisiloxane and Assist® (BASF) 17% surfactant blend in 83%paraffin based mineral oil.

One method of seed treatment is by spraying or dusting the seed with acompound of the invention (i.e. as a formulated composition) beforesowing the seeds. Compositions formulated for seed treatment generallycomprise a film former or adhesive agent. Therefore typically a seedcoating composition of the present invention comprises a biologicallyeffective amount of a compound of Formula 1 and a film former oradhesive agent. Seed can be coated by spraying a flowable suspensionconcentrate directly into a tumbling bed of seeds and then drying theseeds. Alternatively, other formulation types such as wetted powders,solutions, suspoemulsions, emulsifiable concentrates and emulsions inwater can be sprayed on the seed. This process is particularly usefulfor applying film coatings on seeds. Various coating machines andprocesses are available to one skilled in the art. Suitable processesinclude those listed in P. Kosters et al., Seed Treatment: Progress andProspects, 1994 BCPC Mongraph No. 57, and references listed therein.

For further information regarding the art of formulation, see T. S.Woods, “The Formulator's Toolbox—Product Forms for Modern Agriculture”in Pesticide Chemistry and Bioscience, The Food-Environment Challenge,T. Brooks and T. R. Roberts, Eds., Proceedings of the 9th InternationalCongress on Pesticide Chemistry, The Royal Society of Chemistry,Cambridge, 1999, pp. 120-133. See also U.S. Pat. No. 3,235,361, Col. 6,line 16 through Col. 7, line 19 and Examples 10-41; U.S. Pat. No.3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12,15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182;U.S. Pat. No. 2,891,855, Col. 3, line 66 through Col. 5, line 17 andExamples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons,Inc., New York, 1961, pp 81-96; Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989; and Developmentsin formulation technology, PJB Publications, Richmond, UK, 2000.

In the following Examples, all percentages are by weight and allformulations are prepared in conventional ways. Compound numbers referto compounds in Index Tables A-F. Without further elaboration, it isbelieved that one skilled in the art using the preceding description canutilize the present invention to its fullest extent. The followingExamples are, therefore, to be constructed as merely illustrative, andnot limiting of the disclosure in any way whatsoever. Percentages are byweight except where otherwise indicated.

Example A

High Strength Concentrate Compound 3 98.5% silica aerogel  0.5%synthetic amorphous fine silica  1.0%

Example B

Wettable Powder Compound 12 65.0% dodecylphenol polyethylene glycolether  2.0% sodium ligninsulfonate  4.0% sodium silicoaluminate  6.0%montmorillonite (calcined) 23.0%

Example C

Granule Compound 3 10.0% attapulgite granules (low volatile matter,0.71/0.30 mm; 90.0% U.S.S. No. 25-50 sieves)

Example D

Extruded Pellet Compound 12 25.0% anhydrous sodium sulfate 10.0% crudecalcium ligninsulfonate  5.0% sodium alkylnaphthalenesulfonate  1.0%calcium/magnesium bentonite 59.0%

Example E

Emulsifiable Concentrate Compound 3 10.0% polyoxyethylene sorbitolhexoleate 20.0% C₆-C₁₀ fatty acid methyl ester 70.0%

Example F

Microemulsion Compound 12  5.0% polyvinylpyrrolidone-vinyl acetatecopolymer 30.0% alkylpolyglycoside 30.0% glyceryl monooleate 15.0% water20.0%

Example G

Seed Treatment Compound 3 20.00%  polyvinylpyrrolidone-vinyl acetatecopolymer 5.00% montan acid wax 5.00% calcium ligninsulfonate 1.00%polyoxyethylene/polyoxypropylene block copolymers 1.00% stearyl alcohol(POE 20) 2.00% polyorganosilane 0.20% colorant red dye 0.05% water65.75% 

Example H

Fertilizer Stick compound 3  2.50% pyrrolidone-styrene copolymer  4.80%tristyrylphenyl 16-ethoxylate  2.30% talc  0.80% corn starch  5.00%slow-release fertilizer 36.00% kaolin 38.00% water 10.60%

Example I

Suspension Concentrate compound 12  35% butylpolyoxyethylene/polypropylene block copolymer 4.0% stearicacid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0%xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%1,2-benzisothiazolin-3-one 0.1% water 53.7% 

Example J

Emulsion in Water compound 3 10.0%  butyl polyoxyethylene/polypropyleneblock copolymer 4.0% stearic acid/polyethylene glycol copolymer 1.0%styrene acrylic polymer 1.0% xanthan gum 0.1% propylene glycol 5.0%silicone based defoamer 0.1% 1,2-benzisothiazolin-3-one 0.1% aromaticpetroleum based hydrocarbon 20.0 water 58.7% 

Example K

Oil Dispersion compound 12  25% polyoxyethylene sorbitol hexaoleate  15%organically modified bentonite clay 2.5% fatty acid methyl ester 57.5% 

Example L

Suspoemulsion compound 3 10.0%  imidacloprid 5.0% butylpolyoxyethylene/polypropylene block copolymer 4.0% stearicacid/polyethylene glycol copolymer 1.0% styrene acrylic polymer 1.0%xanthan gum 0.1% propylene glycol 5.0% silicone based defoamer 0.1%1,2-benzisothiazolin-3-one 0.1% aromatic petroleum based hydrocarbon20.0%  water 53.7% 

Water-soluble and water-dispersible formulations are typically dilutedwith water to form aqueous compositions before application. Aqueouscompositions for direct applications to the plant or portion thereof(e.g., spray tank compositions) typically contain at least about 1 ppmor more (e.g., from 1 ppm to 100 ppm) of the compound(s) of thisinvention.

Seed is normally treated at a rate of from about 0.001 g (more typicallyabout 0.1 g) to about 10 g per kilogram of seed (i.e. from about 0.0001to 1% by weight of the seed before treatment). A flowable suspensionformulated for seed treatment typically comprises from about 0.5 toabout 70% of the active ingredient, from about 0.5 to about 30% of afilm-forming adhesive, from about 0.5 to about 20% of a dispersingagent, from 0 to about 5% of a thickener, from 0 to about 5% of apigment and/or dye, from 0 to about 2% of an antifoaming agent, from 0to about 1% of a preservative, and from 0 to about 75% of a volatileliquid diluent.

The compounds of this invention are useful as plant disease controlagents. The present invention therefore further comprises a method forcontrolling plant diseases caused by fungal plant pathogens comprisingapplying to the plant or portion thereof to be protected, or to theplant seed to be protected, an effective amount of a compound of theinvention or a fungicidal composition containing said compound. Thecompounds and/or compositions of this invention provide control ofdiseases caused by a broad spectrum of fungal plant pathogens in theAscomycota, Basidiomycota, Zygomycota phyla, and the fungal-likeOomycata class. They are effective in controlling a broad spectrum ofplant diseases, particularly foliar pathogens of ornamental, turf,vegetable, field, cereal, and fruit crops. These pathogens include butare not limited to those listed in Table 1. For Ascomycetes andBasidiomycetes, names for both the sexual/teleomorph/perfect stage aswell as names for the asexual/anamorph/imperfect stage (in parentheses)are listed where known. Synonymous names for pathogens are indicated byan equal sign. For example, the sexual/teleomorph/perfect stage namePhaeosphaeria nodorum is followed by the correspondingasexual/anamorph/imperfect stage name Stagnospora nodorum and thesynonymous older name Septoria nodorum.

TABLE 1 Ascomycetes in the order Pleosporales including Alternariasolani, A. alternate and A. brassicae, Guignardia bidwellii, Venturiainaequalis, Pyrenophora tritici-repentis (Dreschlera tritici-repentis =Helminthosporium tritici-repentis) and Pyrenophora teres (Dreschlerateres = Helminthosporium teres), Corynespora cassiicola, Phaeosphaerianodorum (Stagonospora nodorum = Septoria nodorum), Cochliobolus carbonumand C. heterostrophus, Leptosphaeria biglobosa and L. maculans;Ascomycetes in the order Mycosphaerellales including Mycosphaerellagraminicola (Zymoseptoria tritici = Septoria tritici), M. berkeleyi(Cercosporidium personatum), M. arachidis (Cercospora arachidicola),Passalora sojina (Cercospora sojina), Cercospora zeae-maydis and C.beticola; Ascomycetes in the order Erysiphales (the powdery mildews)such as Blumeria graminis f.sp. tritici and Blumeria graminis f.sp.hordei, Erysiphe polygoni, E. necator (=Uncinula necator), Podosphaerafuliginea (=Sphaerotheca fuliginea), and Podosphaera leucotricha(=Sphaerotheca fuliginea); Ascomycetes in the order Helotiales such asBotryotinia fuckeliana (Botrytis cinerea), Oculimacula yallundae(=Tapesia yallundae; anamorph Helgardia herpotrichoides =Pseudocercosporella herpetrichoides), Monilinia fructicola, Sclerotiniasclerotiorum, Sclerotinia minor, and Sclerotinia homoeocarpa;Ascomycetes in the order Hypocreales such as Giberella zeae (Fusariumgraminearum), G. monoliformis (Fusarium moniliforme), Fusarium solaniand Verticillium dahliae; Ascomycetes in the order Eurotiales such asAspergillus flavus and A. parasiticus; Ascomycetes in the orderDiaporthales such as Cryptosphorella viticola (=Phomopsis viticola),Phomopsis longicolla, and Diaporthe phaseolorum; Other Ascomycetepathogens including Magnaporthe grisea, Gaeumannomyces graminis,Rhynchosporium secalis, and anthracnose pathogens such as Glomerellaacutata (Colletotrichum acutatum), G. graminicola (C. graminicola) andG. lagenaria (C. orbiculare); Basidiomycetes in the order Urediniales(the rusts) including Puccinia recondite, P. striiformis, Pucciniahordei, P. graminis and P. arachidis), Hemileia vastatrix and Phakopsorapachyrhizi; Basidiomycetes in the order Ceratobasidiales such asThanatophorum cucumeris (Rhizoctonia solani) and Ceratobasidiumoryzae-sativae (Rhizoctonia oryzae); Basidiomycetes in the orderPolyporales such as Athelia rolfsii (Sclerotium rolfsii); Basidiomycetesin the order Ustilaginales such as Ustilago maydis; Zygomycetes in theorder Mucorales such as Rhizopus stolonifer; Oomycetes in the orderPythiales, including Phytophthora infestans, P. megasperma, P.parasitica, P. sojae, P. cinnamomi and P. capsici, and Pythium pathogenssuch as Pythium aphanidermatum, P. graminicola, P. irregulare, P.ultimum and P. dissoticum; Oomycetes in the order Peronosporales such asPlasmopara viticola, P. halstedii, Peronospora hyoscyami (=Peronosporatabacina), P. manshurica, Hyaloperonospora parasitica (=Peronosporaparasitica), Pseudoperonospora cubensis and Bremia lactucae; and othergenera and species closely related to all of the above pathogens.

The compounds of the invention are believed to provide protection fromfungal plant pathogens by inhibiting Complex II (succinatedehydrogenase) fungal respiration by disrupting a key enzyme in theKrebs Cycle (TCA cycle) named succinate dehydrogenase (SDH). SDH iscomposed of four nuclear-encoded polypeptides, identified as SDHA, SDHB,SDHC and SDHD. Inhibiting respiration prevents the fungus from makingATP, and thus inhibits growth and reproduction. At the molecular level,carboxamides inhibit ubiquinone reduction by binding to the ubiquinonebinding site (Q_(p) site) formed by subunits SDHB, SDHC and SDHD in theSDH enzyme. The Fungicide Resistance Action Committee (FRAC) hasidentified chemical compounds having this fungicidal mode of action as“SDHIs” as an abbreviation for succinate dehydrogenase inhibitors andcategorized them with FRAC Code 7.

A variety of mutations in subunits SDHB, SDHC and SDHD forming theubiquinone binding site are now known to cause resistance to SDHIs. FRAChas published on their website a “List of fungal species with resistancereports towards SDHI fungicides and mutations in the succinatedehydrogenates gene (updated March 2012)”(http://frac.info/frac/work/List%20of%20SDHI %20resistant%20species.pdfavailable as of 28 Jun. 2012), which includes both mutants produced inthe laboratory through artificial mutagenesis and naturally occurringmutants found in the field showing resistance to SDHIs. Scalliet et al.,“Mutagenesis and Functional Studies with Succinate DehydrogenaseInhibitors in the Wheat Pathogen Mycosphaerella graminicola”, PLoS ONE,2012, 7 (4), 1-20 (published in Adobe Acrobat file format asjournal.pone.0035429.pdf and available throughhttp://www.plosone.org/article/info%3Adoi%2F10.1371%2Fjournal.pone.0035429on 28 Jun. 2012) describes additional mutants of Mycosphaerellagraminicola. These publications disclose fungal pathogens having knownresistant mutants include Alternaria alternata (SDHB: H277Y, H277R;SDHC: H134R; SDHD: D123E, H133R), Aspergillus oryzae (SDHB: H249Y,H249L, H249N; SDHC: T90I; SDHD: D124E), Botrytis cinearea (SDHB: P225L,P225T, P225F, H272Y, H272R, H272L, N230I; SDHD: H132R), Botrytiselliptica (SDHB: H272Y, H272R), Corynespora cassiicola (SDHB: H287Y,H287R; SDHC: S73P, SDHD: S89P), Didymella bryoniae (SDHB: H277R, H277Y),Mycosphaerella graminicola (SDHB: S218F, P220T, P220L, S221P, N225H,N225I, R265P, H267L, H267N, H267R, H267Q, H267Y, I269V, N271K; SDHC:T79I, S83G, A84V, A84I, L85P, N86K, R87C, V88D, H145R, H152R; SDHD:D129E, D129G, D129S, D129T, H139E), Podosphaera xanthii (SDHB: H[???]Y),Sclerotinia sclerotiorum (SDHD: H132R), Ustilago maydis (SDHB: H257L),Stemphylium botryose (SDHB: P225L, H272Y, H272R) and Ustilago maydis(SDHB: H257L), wherein the left letter identifies the amino acid in theprevalent wild-type enzyme subunit, the number specifies the amino acidlocation in the subunit, and the right letter identifies the amino acidin the mutant subunit (the amino acids are identified by standard singleletter codes; see for examplehttp://www.bio.davidson.edu/Biology/aatable.html, accessed 28 Jun.2012). Because the metabolism of other fungal pathogens, such asSeptoria tritici, also involve succinate dehydrogenase, SDHI-resistantmutants are possible for them as well.

Remarkably, compounds of the present invention, retain sufficientactivity against mutant fungal pathogens highly resistant to otherSDHIs, so that the present compounds remain agronomically useful forprotecting plants against the mutant as well as wild-type pathogens. Theimproved efficacy of the present compounds compared to other SDHIfungicides for controlling plant disease caused by the SDHI-resistantfungal pathogens can be determined by simple plant disease controltesting, for example tests similar to Tests A-E disclosed herein, butusing SDHI-resistant instead of wild-type fungal pathogens.

In addition to their fungicidal activity, the compositions orcombinations also have activity against bacteria such as Erwiniaamylovora, Xanthomonas campestris, Pseudomonas syringae, and otherrelated species. By controlling harmful microorganisms, the compounds ofthe invention are useful for improving (i.e. increasing) the ratio ofbeneficial to harmful microorganisms in contact with crop plants ortheir propagules (e.g., seeds, corms, bulbs, tubers, cuttings) or in theagronomic environment of the crop plants or their propagules.

Compounds of the invention are useful in treating all plants, plantparts and seeds. Plant and seed varieties and cultivars can be obtainedby conventional propagation and breeding methods or by geneticengineering methods. Genetically modified plants or seeds (transgenicplants or seeds) are those in which a heterologous gene (transgene) hasbeen stably integrated into the plant's or seed's genome. A transgenethat is defined by its particular location in the plant genome is calleda transformation or transgenic event.

Genetically modified plant cultivars which can be treated according tothe invention include those that are resistant against one or morebiotic stresses (pests such as nematodes, insects, mites, fungi, etc.)or abiotic stresses (drought, cold temperature, soil salinity, etc.), orthat contain other desirable characteristics. Plants can be geneticallymodified to exhibit traits of, for example, herbicide tolerance,insect-resistance, modified oil profiles or drought tolerance. Usefulgenetically modified plants containing single gene transformation eventsor combinations of transformation events are listed in Table 2.Additional information for the genetic modifications listed in Table 2can be obtained from publicly available databases maintained, forexample, by the U.S. Department of Agriculture.

The following abbreviations, T1 through T37, are used in Table 2 fortraits. A “-” means the entry is not available.

Trait Description T1 Glyphosate tolerance T2 High lauric acid oil T3Glufosinate tolerance T4 Phytate breakdown T5 Oxynil tolerance T6Disease resistance T7 Insect resistance T9 Modified flower color T11 ALSherbicide tol. T12 Dicamba tolerance T13 Anti-allergy T14 Salt toleranceT15 Cold tolerance T16 Imidazolinone herbicide tol. T17 Modifiedalpha-amylase T18 Pollination control T19 2,4-D tolerance T20 Increasedlysine T21 Drought tolerance T22 Delayed ripening/senescence T23Modified product quality T24 High cellulose T25 Modifiedstarch/carbohydrate T26 Insect & disease resist. T27 High tryptophan T28Erect leaves semidwarf T29 Semidwarf T30 Low iron tolerance T31 Modifiedoil/fatty acid T32 HPPD tolerance T33 High oil T34 Aryloxyalkanoate tol.T35 Mesotrione tolerance T36 Reduced nicotine T37 Modified product

TABLE 2 Crop Event Name Event Code Trait(s) Gene(s) Alfalfa J101MON-00101-8 T1 cp4 epsps (aroA:CP4) Alfalfa J163 MON-ØØ163-7 T1 cp4epsps (aroA:CP4) Canola* 23-18-17 (Event 18) CGN-89465-2 T2 te Canola*23-198 (Event 23) CGN-89465-2 T2 te Canola* 61061 DP-Ø61Ø61-7 T1 gat4621Canola* 73496 DP-Ø73496-4 T1 gat4621 Canola* GT200 (RT200) MON-89249-2T1 cp4 epsps (aroA:CP4); goxv247 Canola* GT73 (RT73) MON-ØØØ73- T1 cp4epsps (aroA:CP4); goxv247 7 Canola* HCN10 (Topas — T3 bar 19/2) Canola*HCN28 (T45) ACS-BNØØ8-2 T3 pat (syn) Canola* HCN92 (Topas ACS-BNØØ7-1 T3bar 19/2) Canola* MON88302 MON-883Ø2-9 T1 cp4 epsps (aroA:CP4) Canola*MPS961 — T4 phyA Canola* MPS962 — T4 phyA Canola* MPS963 — T4 phyACanola* MPS964 — T4 phyA Canola* MPS965 — T4 phyA Canola* MS1 (B91-4)ACS-BNØØ4-7 T3 bar Canola* MS8 ACS-BNØØ5-8 T3 bar Canola* OXY-235ACS-BNØ11-5 T5 bxn Canola* PHY14 — T3 bar Canola* PHY23 — T3 bar Canola*PHY35 — T3 bar Canola* PHY36 — T3 bar Canola* RF1 (B93-101) ACS-BNØØ1-4T3 bar Canola* RF2 (B94-2) ACS-BNØØ2-5 T3 bar Canola* RF3 ACS-BNØØ3-6 T3bar Bean EMBRAPA 5.1 EMB-PV05 1-1 T6 ac1 (sense and antisense) Brinjal#EE-1 — T7 cry1Ac Carnation 11 (7442) FLO-07442-4 T8; T9 surB; dfr; hfl(f3′5′h) Carnation 11363 (1363A) FLO-11363-1 T8; T9 surB; dfr; bp40(f3′5′h) Carnation 1226A (11226) FLO-11226-8 T8; T9 surB; dfr; bp40(f3′5′h) Carnation 123.2.2 (40619) FLO-4Ø619-7 T8; T9 surB; dfr; hfl(f3′5′h) Carnation 123.2.38 (40644) FLO-4Ø644-4 T8; T9 surB; dfr; hfl(f3′5′h) Carnation 123.8.12 FLO-4Ø689-6 T8; T9 surB; dfr; bp40 (f3′5′h)Carnation 123.8.8 (40685) FLO-4Ø685-1 T8; T9 surB; dfr; bp40 (f3′5′h)Carnation 1351A (11351) FLO-11351-7 T8; T9 surB; dfr; bp40 (f3′5′h)Carnation 1400A (11400) FLO-114ØØ-2 T8; T9 surB; dfr; bp40 (f3′5′h)Carnation 15 FLO-ØØØ15-2 T8; T9 surB; dfr; hfl (f3′5′h) Carnation 16FLO-ØØØ16-3 T8; T9 surB; dfr; hfl (f3′5′h) Carnation 4 FLO-ØØØØ4-9 T8;T9 surB; dfr; hfl (f3′5′h) Carnation 66 FLO-ØØØ66-8  T8; T10 surB; accCarnation 959A (11959) FLO-11959-3 T8; T9 surB; dfr; bp40 (f3′5′h)Carnation 988A (11988) FLO-11988-7 T8; T9 surB; dfr; bp40 (f3′5′h)Carnation 26407 IFD-26497-2 ST8; T9 surB; dfr; bp40 (f3′5′h) Carnation25958 IFD-25958-3 T8; T9 surB; dfr; bp40 (f3′5′h) Chicory RM3-3 — T3 barChicory RM3-4 — T3 bar Chicory RM3-6 — T3 bar Cotton 19-51a DD-Ø1951A-7 T11 S4-HrA Cotton 281-24-236 DAS-24236-5 T3; T7 pat (syn); cry1F Cotton3006-210-23 DAS-21Ø23-5 T3; T7 pat (syn); cry1Ac Cotton 31707 — T5; T7bxn; cry1Ac Cotton 31803 — T5; T7 bxn; cry1Ac Cotton 31807 — T5; T7 bxn;cry1Ac Cotton 31808 — T5; T7 bxn; cry1Ac Cotton 42317 — T5; T7 bxn;cry1Ac Cotton BNLA-601 — T7 cry1Ac Cotton BXN10211 BXN10211-9 T5 bxn;cry1Ac Cotton BXN10215 BXN10215-4 T5 bxn; cry1Ac Cotton BXN10222BXN10222-2 T5 bxn; cry1Ac Cotton BXN10224 BXN10224-4 T5 bxn; cry1AcCotton COT102 SYN-IR102-7 T7 vip3A(a) Cotton COT67B SYN-IR67B-1 T7cry1Ab Cotton COT202 — T7 vip3A Cotton Event 1 — T7 cry1Ac Cotton GMFCry1A GTL-GMF311- T7 cry1Ab-Ac 7 Cotton GHB119 BCS-GH005-8 T7 cry2AeCotton GHB614 BCS-GH002-5 T1 2mepsps Cotton GK12 — T7 cry1Ab-Ac CottonLLCotton25 ACS-GH001-3 T3 bar Cotton MLS 9124 — T7 cry1C Cotton MON1076MON-89924-2 T7 cry1Ac Cotton MON1445 MON-01445-2 T1 cp4 epsps (aroA:CP4)Cotton  MON15985 MON-15985-7 T7 cry1Ac; cry2Ab2 Cotton MON1698MON-89383-1 T7 cp4 epsps (aroA:CP4) Cotton MON531 MON-00531-6 T7 cry1AcCotton MON757 MON-00757-7 T7 cry1Ac Cotton MON88913 MON-88913-8 T1 cp4epsps (aroA:CP4) Cotton Nqwe Chi 6 Bt — T7 — Cotton SKG321 — T7 cry1A;CpTI Cotton T303-3 BCS-GH003-6 T7; T3 cry1Ab; bar Cotton T304-40BCS-GH004-7 T7; T3 cry1Ab; bar Cotton CE43-67B — T7 cry1Ab CottonCE46-02A — T7 cry1Ab Cotton CE44-69D — T7 cry1Ab Cotton 1143-14A — T7cry1Ab Cotton 1143-51B — T7 cry1Ab Cotton T342-142 — T7 cry1Ab CottonPV-GHGT07 — T1 cp4 epsps (aroA:CP4) (1445) Cotton EE-GH3 — T1 mepspsCotton EE-GH5 — T7 cry1Ab Cotton MON88701 MON-88701-3 T12; T3 Modifieddmo; bar Cotton OsCr11 —  T13 Modified Cry j Creeping ASR368 SMG-368ØØ-2T1 cp4 epsps (aroA:CP4) Bentgrass Eucalyptus 20-C —  T14 codA Eucalyptus12-5C —  T14 codA Eucalyptus 12-5B —  T14 codA Eucalyptus 107-1 —  T14codA Eucalyptus Jan. 9, 2001 —  T14 codA Eucalyptus Feb. 1, 2001 —  T14codA Eucalyptus —  T15 des9 Flax FP967 CDC-FL001-2  T11 als Lentil RH44—  T16 als Maize 3272 SYN-E3272-5  T17 amy797E Maize 5307 SYN-05307-1 T7ecry3.1Ab Maize 59122 DAS-59122-7 T7; T3 cry34Ab1; cry35Ab1; pat Maize676 PH-000676-7 T3; T18 pat; dam Maize 678 PH-000678-9 T3; T18 pat; damMaize 680 PH-000680-2 T3; T18 pat; dam Maize 98140 DP-098140-6 T1; T11gat4621; zm-hra Maize Bt10 — T7; T3 cry1Ab; pat Maize Bt176 (176)SYN-EV176-9 T7; T3 cry1Ab; bar Maize BVLA430101 — T4 phyA2 Maize CBH-351ACS-ZMO04-3 T7; T3 cry9C; bar Maize DAS40278-9 DAS40278-9  T19 aad-1Maize DBT418 DKB-89614-9 T7; T3 cry1Ac; pinII; bar Maize DLL25 (B16)DKB-89790-5 T3 bar Maize GA21 MON-00021-9 T1 mepsps Maize GG25 — T1mepsps Maize GJ11 — T1 mepsps Maize F1117 — T1 mepsps Maize GAT-ZM1 — T3pat Maize LY038 REN-00038-3  T20 cordapA Maize MIR162 SYN-IR162-4 T7vip3Aa20 Maize MIR604 SYN-IR604-5 T7 mcry3A Maize MON801 MON801 T7; T1cry1Ab; cp4 epsps (aroA:CP4); (MON80100) goxv247 Maize MON802MON-80200-7 T7; T1 cry1Ab; cp4 epsps (aroA:CP4); goxv247 Maize MON809PH-MON-809- T7; T1 cry1Ab; cp4 epsps (aroA:CP4); 2 goxv247 Maize MON810MON-00810-6 T7; T1 cry1Ab; cp4 epsps (aroA:CP4); goxv247 Maize MON832 —T1 cp4 epsps (aroA:CP4); goxv247 Maize MON863 MON-00863-5 T7 cry3Bb1Maize  MON87427 MON-87427-7 T1 cp4 epsps (aroA:CP4) Maize  MON87460MON-87460-4  T21 cspB Maize  MON88017 MON-88017-3 T7; T1 cry3Bb1; cp4epsps (aroA:CP4) Maize  MON89034 MON-89034-3 T7 cry2Ab2; cry1A.105 MaizeMS3 ACS-ZMO01-9 T3; T18 bar; bar-se Maize MS6 ACS-ZMO05-4 T3; T18 bar;bar-se Maize NK603 MON-00603-6 T1 cp4 epsps (aroA:CP4) Maize T14ACS-ZMO02-1 T3 pat (syn) Maize T25 ACS-ZMO03-2 T3 pat (syn) Maize TC1507DAS-01507-1 T7; T3 crylFa2; pat Maize TC6275 DAS-06275-8 T7; T3 mocry1F;bar Maize VIP1034 T7; T3 vip3A; pat Maize 43A47 DP-043A47-3 T7; T3cry1F; cry34Ab1; cry35Ab1; pat Maize 40416 DP-040416-8 T7; T3 cry1F;cry34Ab1; cry35Ab1; pat Maize 32316 DP-032316-8 T7; T3 cry1F; cry34Ab1;cry35Ab1; pat Maize 4114 DP-004114-3 T7; T3 cry1F; cry34Ab1; cry35Ab1;pat Melon Melon A —  T22 sam-k Melon Melon B —  T22 sam-k Papaya 55-1CUH-CP551-8 T6 prsv cp Papaya 63-1 CUH-CP631-7 T6 prsv cp Papaya HuanongNo. 1 — T6 prsv rep Papaya X17-2 UFL-X17CP-6 T6 prsv cp PetuniaPetunia-CHS —  T25 CHS suppression Plum C-5 ARS-PLMC5-6 T6 ppv cpCanola** ZSR500 — T1 cp4 epsps (aroA:CP4); goxv247 Canola** ZSR502 — T1cp4 epsps (aroA:CP4); goxv247 Canola** ZSR503 — T1 cp4 epsps (aroA:CP4);goxv247 Poplar Bt poplar — T7 cry1Ac; API Poplar Hybrid poplar clone —T7 cry1Ac; API 741 Poplar trg300-1 —  T24 AaXEG2 Poplar trg300-2 —  T24AaXEG2 Potato 1210 amk — T7 cry3A Potato 2904/1 kgs — T7 cry3A Canola**ZSR500 — T1 cp4 epsps (aroA:CP4); goxv247 Canola** ZSR502 — T1 cp4 epsps(aroA:CP4); goxv247 Potato ATBT04-27 NMK-89367-8 T7 cry3A PotatoATBT04-30 NMK-89613-2 T7 cry3A Potato ATBT04-31 NMK-89170-9 T7 cry3APotato ATBT04-36 NMK-89279-1 T7 cry3A Potato ATBT04-6 NMK-89761-6 T7cry3A Potato BT06 NMK-89812-3 T7 cry3A Potato BT10 NMK-89175-5 T7 cry3APotato BT12 NMK-89601-8 T7 cry3A Potato BT16 NMK-89167-6 T7 cry3A PotatoBT17 NMK-89593-9 T7 cry3A Potato BT18 NMK-89906-7 T7 cry3A Potato BT23NMK-89675-1 T7 cry3A Potato EH92-527-1 BPS-25271-9  T25 gbss (antisense)Potato HLMT15-15 — T7; T6 cry3A; pvy cp Potato HLMT15-3 — T7; T6 cry3A;pvy cp Potato HLMT15-46 — T7; T6 cry3A; pvy cp Potato RBMT15-101NMK-89653-6 T7; T6 cry3A; pvy cp Potato RBMT21-129 NMK-89684-1 T7; T6cry3A; plry orf1; plry orf2 Potato RBMT21-152 — T7; T6 cry3A; plry orf1;plry orf2 Potato RBMT21-350 NMK-89185-6 T7; T6 cry3A; plry orf1; plryorf2 Potato RBMT22-082 NMK-89896-6 T7; T6.; T1 cry3A; plry orf1; plryorf2; cp4 epsps (aroA:CP4) Potato RBMT22-186 — T7; T6.; T1 cry3A; plryorf1; plry orf2; cp4 epsps (aroA:CP4) Potato RBMT22-238 — T7; T6.; T1cry3A; plry orf1; plry orf2; cp4 epsps (aroA:CP4) Potato RBMT22-262 —T7; T6.; T1 cry3A; plry orf1; plry orf2; cp4 epsps (aroA:CP4) PotatoSEMT15-02 NMK-89935-9 T7; T6 cry3A; pvy cp Potato SEMT15-07 — T7; T6cry3A; pvy cp Potato SEMT15-15 NMK-89930-4 T7; T6 cry3A; pvy cp PotatoSPBT02-5 NMK-89576-1 T7 cry3A Potato SPBT02-7 NMK-89724-5 T7 cry3A Rice7Crp#242-95-7 —  T13 7crp Rice 7Crp#10 —  T13 7crp Rice GM Shanyou 63 —T7 cry1Ab; cry1Ac Rice Huahui-1/TT51 -1 — T7 cry1Ab; cry1Ac RiceLLRICE06 ACS-OS001-4 T3 bar Rice LLRICE601 BCS-OS003-7 T3 bar RiceLLRICE62 ACS-OS002-5 T3 bar Rice Tarom molaii + — T7 cry1Ab (truncated)cry1Ab Rice GAT-OS2 — T3 bar Rice GAT-OS3 — T3 bar Rice PE-7 — T7 Cry1AcRice 7Crp#10 —  T13 7crp Rice KPD627-8 —  T27 OASA1D Rice KPD722-4 — T27 OASA1D Rice KA317 —  T27 OASA1D Rice HW5 —  T27 OASA1D Rice HW1 — T27 OASA1D Rice B-4-1-18 —  T28 Δ OsBRI1 Rice G-3-3-22 —  T29 OSGA2ox1Rice AD77 — T6 DEF Rice AD51 — T6 DEF Rice AD48 — T6 DEF Rice AD41 — T6DEF Rice 13p-s-atAprt1 —  T30 Hv-S1; Hv-AT-A; APRT Rice 13pAprt1 —  T30APRT Rice gHv-S1-gHv-AT-1 —  T30 Hv-S1; Hv-AT-A; Hv-AT-B Rice gHvIDS3-1—  T30 HvIDS3 Rice gHv-AT1 —  T30 Hv-AT-A; Hv-AT-B Rice gHv-S1-1 —  T30Hv-S1 Rice NIA-OS006-4 — T6 WRKY45 Rice NIA-OS005-3 — T6 WRKY45 RiceNIA-OS004-2 — T6 WRKY45 Rice NIA-OS003-1 — T6 WRKY45 Rice NIA-OS002-9 —T6 WRKY45 Rice NIA-OS001-8 — T6 WRKY45 Rice OsCr11 —  T13 Modified Cry jRice 17053 — T1 cp4 epsps (aroA:CP4) Rice 17314 — T1 cp4 epsps(aroA:CP4) Rose WKS82/130-4-1 IFD-52401-4 T9 5AT; bp40 (f3′5′h) RoseWKS92/130-9-1 IFD-52901-9 T9 5AT; bp40 (f3′5′h) Soybean 260-05 (G94-1, —T9 gm-fad2-1 (silencing locus) G94-19, G168) Soybean A2704-12ACS-GM005-3 T3 pat Soybean A2704-21 ACS-GM004-2 T3 pat Soybean A5547-127ACS-GM006-4 T3 pat Soybean A5547-35 ACS-GM008-6 T3 pat Soybean CV127BPS-CV127-9  T16 csr1-2 Soybean DAS68416-4 DAS68416-4 T3 pat SoybeanDP305423 DP-305423-1 T31; T11 gm-fad2-1 (silencing locus); gm-hraSoybean DP356043 DP-356043-5 T31; T1 gm-fad2-1 (silencing locus);gat4601 Soybean FG72 MST-FG072-3 T1; T32 2mepsps; hppdPF W336 SoybeanGTS 40-3-2 (40-3- MON-04032-6 T1 cp4 epsps (aroA:CP4) 2) Soybean GU262ACS-GM003-1 T3 pat Soybean MON87701 MON-87701-2 T7 cry1Ac SoybeanMON87705 MON-87705-6 T31; T1 fatbl-A (sense & antisense); fad2- 1A(sense & antisense); cp4 epsps (aroA:CP4) Soybean MON87708 MON-87708-9T12; T1 dmo; cp4 epsps (aroA:CP4) Soybean MON87769 MON-87769-7 T31; T1Pj.D6D; Nc.Fad3; cp4 epsps (aroA:CP4) Soybean MON89788 MON-89788-1 T1cp4 epsps (aroA:CP4) Soybean W62 ACS-GM002-9 T3 bar Soybean W98ACS-GM001-8 T3 bar Soybean MON87754 MON-87754-1  T33 dgat2A SoybeanDAS21606 DAS-21606 T34; T3 Modified aad-12; pat Soybean DAS44406DAS-44406-6 T34; T1; T3 Modified aad-12; 2mepsps; pat Soybean SYHT04RSYN-0004R-8  T35 Modified avhppd Soybean 9582.814.19.1 T7; T3 cry1Ac;cry1F; pat Squash CZW3 SEM-ØCZW3- T6 cmv cp; zymv cp; wmv cp 2 SquashZW20 SEM-0ZW20-7 T6 zymv cp, wmv cp Sugar Beet GTSB77 SY-GTSB77-8 T1 cp4epsps (aroA:CP4); goxv247 (T9100152) Sugar Beet H7-1 KM-000H71-4 T1 cp4epsps (aroA:CP4) Sugar Beet T120-7 ACS-BV001-3 T3 pat Sugar Beet T227-1— T1 cp4 epsps (aroA:CP4) Sugarcane NXI-1T —  T21 EcbetA SunflowerX81359 —  T16 als Sweet Pepper PK-SP01 — T6 cmv cp Tobacco C/F/93/08-02— T5 bxn Tobacco Vector 21-41 —  T36 NtQPT1 (antisense) Tomato 1345-4 — T22 acc (truncated) Tomato 35-1-N —  T22 sam-k Tomato 5345 — T7 cry1AcTomato 8338 CGN-89322-3  T22 accd Tomato B SYN-0000B-6  T22 pg (sense orantisense) Tomato Da SYN-0000DA-  T22 pg (sense or antisense) 9Sunflower X81359 —  T16 als Tomato Da Dong No 9 —  T37 — Tomato F(1401F, h38F, SYN-0000F-1  T22 pg (sense or antisense) 11013F,7913F)Tomato FLAVR SAVR ™ CGN-89564-2  T22 pg (sense or antisense) TomatoHuafan No 1 —  T22 anti-efe Tomato PK-TM8805R — T6 cmv cp (8805R) WheatMON71800 MON-718ØØ-3 T1 cp4 epsps (aroA:CP4) *Argentine, **Polish, #Eggplant

Treatment of genetically modified plants and seeds with compounds of theinvention may result in super-additive or synergistic effects. Forexample, reduction in application rates, broadening of the activityspectrum, increased tolerance to biotic/abiotic stresses or enhancedstorage stability may be greater than expected from just simple additiveeffects of the application of compounds of the invention on geneticallymodified plants and seeds.

Compounds of this invention are useful in seed treatments for protectingseeds from plant diseases. In the context of the present disclosure andclaims, treating a seed means contacting the seed with a biologicallyeffective amount of a compound of this invention, which is typicallyformulated as a composition of the invention. This seed treatmentprotects the seed from soil-borne disease pathogens and generally canalso protect roots and other plant parts in contact with the soil of theseedling developing from the germinating seed. The seed treatment mayalso provide protection of foliage by translocation of the compound ofthis invention or a second active ingredient within the developingplant. Seed treatments can be applied to all types of seeds, includingthose from which plants genetically transformed to express specializedtraits will germinate. Representative examples include those expressingproteins toxic to invertebrate pests, such as Bacillus thuringiensistoxin or those expressing herbicide resistance such as glyphosateacetyltransferase, which provides resistance to glyphosate. Seedtreatments with compounds of this invention can also increase vigor ofplants growing from the seed.

Compounds of this invention and their compositions, both alone and incombination with other fungicides, nematicides and insecticides, areparticularly useful in seed treatment for crops including, but notlimited to, maize or corn, soybeans, cotton, cereal (e.g., wheat, oats,barley, rye and rice), potatoes, vegetables and oilseed rape.

Furthermore, the compounds of this invention are useful in treatingpostharvest diseases of fruits and vegetables caused by fungi andbacteria. These infections can occur before, during and after harvest.For example, infections can occur before harvest and then remain dormantuntil some point during ripening (e.g., host begins tissue changes insuch a way that infection can progress); also infections can arise fromsurface wounds created by mechanical or insect injury. In this respect,the compounds of this invention can reduce losses (i.e. losses resultingfrom quantity and quality) due to postharvest diseases which may occurat any time from harvest to consumption. Treatment of postharvestdiseases with compounds of the invention can increase the period of timeduring which perishable edible plant parts (e.g., fruits, seeds,foliage, stems, bulbs, tubers) can be stored refrigerated orun-refrigerated after harvest, and remain edible and free fromnoticeable or harmful degradation or contamination by fungi or othermicroorganisms. Treatment of edible plant parts before or after harvestwith compounds of the invention can also decrease the formation of toxicmetabolites of fungi or other microorganisms, for example, mycotoxinssuch as aflatoxins.

Plant disease control is ordinarily accomplished by applying aneffective amount of a compound of this invention either pre- orpost-infection, to the portion of the plant to be protected such as theroots, stems, foliage, fruits, seeds, tubers or bulbs, or to the media(soil or sand) in which the plants to be protected are growing. Thecompounds can also be applied to seeds to protect the seeds andseedlings developing from the seeds. The compounds can also be appliedthrough irrigation water to treat plants. Control of postharvestpathogens which infect the produce before harvest is typicallyaccomplished by field application of a compound of this invention, andin cases where infection occurs after harvest the compounds can beapplied to the harvested crop as dips, sprays, fumigants, treated wrapsand box liners.

Rates of application for these compounds (i.e. a fungicidally effectiveamount) can be influenced by factors such as the plant diseases to becontrolled, the plant species to be protected, ambient moisture andtemperature and should be determined under actual use conditions. Oneskilled in the art can easily determine through simple experimentationthe fungicidally effective amount necessary for the desired level ofplant disease control. Foliage can normally be protected when treated ata rate of from less than about 1 g/ha to about 5,000 g/ha of activeingredient. Seed and seedlings can normally be protected when seed istreated at a rate of from about 0.001 g (more typically about 0.1 g) toabout 10 g per kilogram of seed.

Compounds of this invention can also be mixed with one or more otherbiologically active compounds or agents including fungicides,insecticides, nematocides, bactericides, acaricides, herbicides,herbicide safeners, growth regulators such as insect molting inhibitorsand rooting stimulants, chemosterilants, semiochemicals, repellents,attractants, pheromones, feeding stimulants, plant nutrients, otherbiologically active compounds or entomopathogenic bacteria, virus orfungi to form a multi-component pesticide giving an even broaderspectrum of agricultural protection. Thus the present invention alsopertains to a composition comprising a compound of Formula 1 (in afungicidally effective amount) and at least one additional biologicallyactive compound or agent (in a biologically effective amount) and canfurther comprise at least one of a surfactant, a solid diluent or aliquid diluent. The other biologically active compounds or agents can beformulated in compositions comprising at least one of a surfactant,solid or liquid diluent. For mixtures of the present invention, one ormore other biologically active compounds or agents can be formulatedtogether with a compound of Formula 1, to form a premix, or one or moreother biologically active compounds or agents can be formulatedseparately from the compound of Formula 1, and the formulations combinedtogether before application (e.g., in a spray tank) or, alternatively,applied in succession.

As mentioned in the Summary of the Invention, one aspect of the presentinvention is a fungicidal composition comprising (i.e. a mixture orcombination of) a compound of Formula 1, an N-oxide, or a salt thereof(i.e. component a), and at least one other fungicide (i.e. component b).Of note is such a combination where the other fungicidal activeingredient has different site of action from the compound of Formula 1.In certain instances, a combination with at least one other fungicidalactive ingredient having a similar spectrum of control but a differentsite of action will be particularly advantageous for resistancemanagement. Thus, a composition of the present invention can furthercomprise a fungicidally effective amount of at least one additionalfungicidal active ingredient having a similar spectrum of control but adifferent site of action.

Of note is a composition which in addition to the Formula 1 compound ofcomponent (a), includes as component (b) at least one fungicidalcompound selected from the group consisting of the FRAC-defined mode ofaction (MOA) classes (A) nucleic acid synthesis, (B) mitosis and celldivision, (C) respiration, (D) amino acid and protein synthesis, (E)signal transduction, (F) lipid synthesis and membrane integrity, (G)sterol biosynthesis in membranes, (H) cell wall biosynthesis inmembranes, (I) melanin synthesis in cell wall, (P) host plant defenseinduction, multi-site contact activity and unknown mode of action.

FRAC-recognized or proposed target sites of action along with their FRACtarget site codes belonging to the above MOA classes are (A1) RNApolymerase I, (A2) adenosine deaminase, (A3) DNA/RNA synthesis(proposed), (A4) DNA topoisomerase, (B1-B3) β-tubulin assembly inmitosis, (B4) cell division (proposed), (B5) delocalization ofspectrin-like proteins, (C1) complex I NADH odxido-reductase, (C2)complex II: succinate dehydrogenase, (C3) complex III: cytochrome bc1(ubiquinol oxidase) at Qo site, (C4) complex III: cytochrome bc1(ubiquinone reductase) at Qi site, (C5) uncouplers of oxidativephosphorylation, (C6) inhibitors of oxidative phosphorylation, ATPsynthase, (C7) ATP production (proposed), (C8) complex III: cytochromebc1 (ubiquinone reductase) at Qx (unknown) site, (D1) methioninebiosynthesis (proposed), (D2-D5) protein synthesis, (E1) signaltransduction (mechanism unknown), (E2-E3) MAP/histidine kinase inosmotic signal transduction, (F2) phospholipid biosynthesis, methyltransferase, (F3) lipid peroxidation (proposed), (F4) cell membranepermeability, fatty acids (proposed), (F6) microbial disrupters ofpathogen cell membranes, (F7) cell membrane disruption (proposed), (G1)C14-demethylase in sterol biosynthesis, (G2) Δ14-reductase andA8→Δ7-isomerase in sterol biosynthesis, (G3) 3-keto reductase,C4-demethylation, (G4) squalene epoxidase in sterol biosynthesis, (H3)trehalase and inositol biosynthesis, (H4) chitin synthase, (H5)cellulose synthase, (I1) reductase in melanin biosynthesis and (I2)dehydratase in melanin biosynthesis.

Of particular note is a composition which in addition to the Formula 1compound of component (a), includes as component (b) at least onefungicidal compound selected from the group consisting of the classes(b1) methyl benzimidazole carbamate (MBC) fungicides; (b2) dicarboximidefungicides; (b3) demethylation inhibitor (DMI) fungicides; (b4)phenylamide fungicides; (b5) amine/morpholine fungicides; (b6)phospholipid biosynthesis inhibitor fungicides; (b7) succinatedehydrogenase inhibitor fungicides; (b8) hydroxy(2-amino-)pyrimidinefungicides; (b9) anilinopyrimidine fungicides; (b10) N-phenyl carbamatefungicides; (b11) quinone outside inhibitor (QoI) fungicides; (b12)phenylpyrrole fungicides; (b13) azanaphthalene fungicides; (b14) lipidperoxidation inhibitor fungicides; (b15) melanin biosynthesisinhibitor-reductase (MBI-R) fungicides; (b16) melanin biosynthesisinhibitor-dehydratase (MBI-D) fungicides; (b17) sterol biosynthesisinhibitor (SBI): Class III fungicides; (b18) squalene-epoxidaseinhibitor fungicides; (b19) polyoxin fungicides; (b20) phenylureafungicides; (b21) quinone inside inhibitor (QiI) fungicides; (b22)benzamide and thiazole carboxamide fungicides; (b23) enopyranuronic acidantibiotic fungicides; (b24) hexopyranosyl antibiotic fungicides; (b25)glucopyranosyl antibiotic: protein synthesis fungicides; (b26)glucopyranosyl antibiotic: trehalase and inositol biosynthesisfungicides; (b27) cyanoacetamideoxime fungicides; (b28) carbamatefungicides; (b29) oxidative phosphorylation uncoupling fungicides; (b30)organo tin fungicides; (b31) carboxylic acid fungicides; (b32)heteroaromatic fungicides; (b33) phosphonate fungicides; (b34)phthalamic acid fungicides; (b35) benzotriazine fungicides; (b36)benzene-sulfonamide fungicides; (b37) pyridazinone fungicides; (b38)thiophene-carboxamide fungicides; (b39) complex I NADH oxidoreductaseinhibitor fungicides; (b40) carboxylic acid amide (CAA) fungicides;(b41) tetracycline antibiotic fungicides; (b42) thiocarbamatefungicides; (b43) benzamide fungicides; (b44) microbial fungicides;(b45) Q_(X)I fungicides; (b46) plant extract fungicides; (b47) hostplant defense induction fungicides; (b48) multi-site contact activityfungicides; (b49) fungicides other than fungicides of classes (b1)through (b48); and salts of compounds of classes (b1) through (b48).

Further descriptions of these classes of fungicidal compounds areprovided below.

(b1) “Methyl benzimidazole carbamate (MBC) fungicides” (FRAC code 1)inhibit mitosis by binding to β-tubulin during microtubule assemblyInhibition of microtubule assembly can disrupt cell division, transportwithin the cell and cell structure. Methyl benzimidazole carbamatefungicides include benzimidazole and thiophanate fungicides. Thebenzimidazoles include benomyl, carbendazim, fuberidazole andthiabendazole. The thiophanates include thiophanate andthiophanate-methyl.

(b2) “Dicarboximide fungicides” (FRAC code 2) inhibit a MAP/histidinekinase in osmotic signal transduction. Examples include chlozolinate,iprodione, procymidone and vinclozolin.

(b3) “Demethylation inhibitor (DMI) fungicides” (FRAC code 3) (SterolBiosynthesis Inhibitors (SBI): Class I) inhibit C14-demethylase, whichplays a role in sterol production. Sterols, such as ergosterol, areneeded for membrane structure and function, making them essential forthe development of functional cell walls. Therefore, exposure to thesefungicides results in abnormal growth and eventually death of sensitivefungi. DMI fungicides are divided between several chemical classes:azoles (including triazoles and imidazoles), pyrimidines, piperazines,pyridines and triazolinthiones. The triazoles include azaconazole,bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole(including diniconazole-M), epoxiconazole, etaconazole, fenbuconazole,fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole,ipconazole, metconazole, myclobutanil, penconazole, propiconazole,quinconazole, simeconazole, tebuconazole, tetraconazole, triadimefon,triadimenol, triticonazole, uniconazole, uniconazole-P,α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol,rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole,rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,andrel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole.The imidazoles include econazole, imazalil, oxpoconazole, prochloraz,pefurazoate and triflumizole. The pyrimidines include fenarimol,nuarimol and triarimol. The piperazines include triforine. The pyridinesinclude buthiobate, pyrifenox, pyrisoxazole(3-[(3R)-5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine,mixture of 3R,5R- and 3R,5S-isomers) and(αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol.The triazolinthiones include prothioconazole and2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione.Biochemical investigations have shown that all of the above mentionedfungicides are DMI fungicides as described by K. H. Kuck et al. inModern Selective Fungicides—Properties, Applications and Mechanisms ofAction, H. Lyr (Ed.), Gustav Fischer Verlag: New York, 1995, 205-258.

(b4) “Phenylamide fungicides” (FRAC code 4) are specific inhibitors ofRNA polymerase in Oomycete fungi. Sensitive fungi exposed to thesefungicides show a reduced capacity to incorporate uridine into rRNA.Growth and development in sensitive fungi is prevented by exposure tothis class of fungicide. Phenylamide fungicides include acylalanine,oxazolidinone and butyrolactone fungicides. The acylalanines includebenalaxyl, benalaxyl-M (also known as kiralaxyl), furalaxyl, metalaxyland metalaxyl-M (also known as mefenoxam). The oxazolidinones includeoxadixyl. The butyrolactones include ofurace.

(b5) “Amine/morpholine fungicides” (FRAC code 5) (SBI: Class II) inhibittwo target sites within the sterol biosynthetic pathway, Δ⁸→Δ⁷ isomeraseand Δ¹⁴ reductase. Sterols, such as ergosterol, are needed for membranestructure and function, making them essential for the development offunctional cell walls. Therefore, exposure to these fungicides resultsin abnormal growth and eventually death of sensitive fungi.Amine/morpholine fungicides (also known as non-DMI sterol biosynthesisinhibitors) include morpholine, piperidine and spiroketal-aminefungicides. The morpholines include aldimorph, dodemorph, fenpropimorph,tridemorph and trimorphamide. The piperidines include fenpropidin andpiperalin. The spiroketal-amines include spiroxamine.

(b6) “Phospholipid biosynthesis inhibitor fungicides” (FRAC code 6)inhibit growth of fungi by affecting phospholipid biosynthesis.Phospholipid biosynthesis fungicides include phophorothiolate anddithiolane fungicides. The phosphorothiolates include edifenphos,iprobenfos and pyrazophos. The dithiolanes include isoprothiolane.

(b7) “Succinate dehydrogenase inhibitor (SDHI) fungicides”” (FRAC code7) inhibit Complex II fungal respiration by disrupting a key enzyme inthe Krebs Cycle (TCA cycle) named succinate dehydrogenase. Inhibitingrespiration prevents the fungus from making ATP, and thus inhibitsgrowth and reproduction. SDHI fungicides include phenylbenzamide, furancarboxamide, oxathiin carboxamide, thiazole carboxamide,pyrazole-4-carboxamide, pyridine carboxamide, phenyl oxoethyl thiopheneamides and pyridinylethyl benzamides The benzamides include benodanil,flutolanil and mepronil. The furan carboxamides include fenfuram. Theoxathiin carboxamides include carboxin and oxycarboxin. The thiazolecarboxamides include thifluzamide. The pyrazole-4-carboxamides includebenzovindiflupyr(N-[9-(dichloromethylene)-1,2,3,4-tetrahydro-1,4-methanonaphthalen-5-yl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide),bixafen, fluxapyroxad(3-(difluoromethyl)-1-methyl-N-(3′,4′,5′-trifluoro[1,1′-biphenyl]-2-yl)-1H-pyrazole-4-carboxamide),furametpyr, isopyrazam(3-(difluoromethyl)-1-methyl-N-[1,2,3,4-tetrahydro-9-(1-methylethyl)-1,4-methanonaphthalen-5-yl]-1H-pyrazole-4-carboxamide),penflufen(N-[2-(1,3-dimethylbutyl)phenyl]-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide),penthiopyrad, sedaxane(N-[2-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide),N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide,N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamideandN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methyl-ethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide.The pyridine carboxamides include boscalid. The phenyl oxoethylthiophene amides include isofetamid(N-[1,1-dimethyl-2-[2-methyl-4-(1-methylethoxy)phenyl]-2-oxoethyl]-3-methyl-2-thiophenecarboxamide).The pyridinylethyl benzamides include fluopyram.

(b8) “Hydroxy-(2-amino-)pyrimidine fungicides” (FRAC code 8) inhibitnucleic acid synthesis by interfering with adenosine deaminase. Examplesinclude bupirimate, dimethirimol and ethirimol.

(b9) “Anilinopyrimidine fungicides” (FRAC code 9) are proposed toinhibit biosynthesis of the amino acid methionine and to disrupt thesecretion of hydrolytic enzymes that lyse plant cells during infection.Examples include cyprodinil, mepanipyrim and pyrimethanil.

(b10) “N-Phenyl carbamate fungicides” (FRAC code 10) inhibit mitosis bybinding to β-tubulin and disrupting microtubule assembly. Inhibition ofmicrotubule assembly can disrupt cell division, transport within thecell and cell structure. Examples include diethofencarb.

(b11) “Quinone outside inhibitor (QoI) fungicides” (FRAC code 11)inhibit Complex III mitochondrial respiration in fungi by affectingubiquinol oxidase. Oxidation of ubiquinol is blocked at the “quinoneoutside” (Q_(o)) site of the cytochrome bc₁ complex, which is located inthe inner mitochondrial membrane of fungi Inhibiting mitochondrialrespiration prevents normal fungal growth and development. Quinoneoutside inhibitor fungicides include methoxyacrylate, methoxycarbamate,oximinoacetate, oximinoacetamide and dihydrodioxazine fungicides(collectively also known as strobilurin fungicides), andoxazolidinedione, imidazolinone and benzylcarbamate fungicides. Themethoxyacrylates include azoxystrobin,coumoxystrobin(methyl(αE)-2-[[(3-butyl-4-methyl-2-oxo-2H-1-benzopyran-7-yl)oxy]methyl]-α-(methoxymethylene)benzeneacetate),enoxastrobin(methyl(αE)-2-[[[(E)-[(2E)-3-(4-chlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxymethylene)benzeneaceate)(also known as enestroburin),flufenoxystrobin(methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate),picoxystrobin, andpyraoxystrobin(methyl(αE)-2-[[[3-(4-chlorophenyl)-1-methyl-1H-pyrazol-5-yl]oxy]methyl]-α-(methoxymethylene)benzeneacetate).The methoxycarbamates include pyraclostrobin, pyrametostrobin(methylN-[2-[[(1,4-dimethyl-3-phenyl-1H-pyrazol-5-yl)oxy]methyl]phenyl]-N-methoxycarbamate)and triclopyricarb(methylN-methoxy-N-[2-[[(3,5,6-trichloro-2-pyridinyl)oxy]methyl]phenyl]carbamate).The oximinoacetates include kresoxim-methyl, and trifloxystrobin. Theoximinoacetamides include dimoxystrobin, fenaminstrobin((αE)-2-[[[(E)-[(2E)-3-(2,6-dichlorophenyl)-1-methyl-2-propen-1-ylidene]amino]oxy]methyl]-α-(methoxyimino)-N-methylbenzeneacetamide),metominostrobin, orysastrobin andα-[methoxyimino]-N-methyl-2-[[[1-[3-(trifluoro-methyl)phenyl]ethoxy]imino]methyl]benzeneacetamide.The dihydrodioxazines include fluoxastrobin. The oxazolidinedionesinclude famoxadone. The imidazolinones include fenamidone. Thebenzylcarbamates include pyribencarb. Class (b11) also includesmandestrobin(2-[(2,5-dimethylphenoxy)methyl]-α-methoxy-N-benzeneacetamide).

(b12) “Phenylpyrrole fungicides” (FRAC code 12) inhibit a MAP/histidinekinase associated with osmotic signal transduction in fungi. Fenpicloniland fludioxonil are examples of this fungicide class.

(b13) “Azanaphthalene fungicides” (FRAC code 13) are proposed to inhibitsignal transduction by a mechanism which is as yet unknown. They havebeen shown to interfere with germination and/or appressorium formationin fungi that cause powdery mildew diseases. Azanaphthalene fungicidesinclude aryloxyquinolines and quinazolinones. The aryloxyquinolinesinclude quinoxyfen. The quinazolinones include proquinazid.

(b14) “Lipid peroxidation inhibitor fungicides” (FRAC code 14) areproposed to inhibit lipid peroxidation which affects membrane synthesisin fungi. Members of this class, such as etridiazole, may also affectother biological processes such as respiration and melanin biosynthesis.Lipid peroxidation fungicides include aromatic hydrocarbon and1,2,4-thiadiazole fungicides. The aromatic hydrocarboncarbon fungicidesinclude biphenyl, chloroneb, dicloran, quintozene, tecnazene andtolclofos-methyl. The 1,2,4-thiadiazoles include etridiazole.

(b15) “Melanin biosynthesis inhibitors-reductase (MBI-R) fungicides”(FRAC code 16.1) inhibit the naphthal reduction step in melaninbiosynthesis. Melanin is required for host plant infection by somefungi. Melanin biosynthesis inhibitors-reductase fungicides includeisobenzofuranone, pyrroloquinolinone and triazolobenzothiazolefungicides. The isobenzofuranones include fthalide. Thepyrroloquinolinones include pyroquilon. The triazolobenzothiazolesinclude tricyclazole.

(b16) “Melanin biosynthesis inhibitors-dehydratase (MBI-D) fungicides”(FRAC code 16.2) inhibit scytalone dehydratase in melanin biosynthesis.Melanin in required for host plant infection by some fungi. Melaninbiosynthesis inhibitors-dehydratase fungicides includecyclopropanecarboxamide, carboxamide and propionamide fungicides. Thecyclopropanecarboxamides include carpropamid. The carboxamides includediclocymet. The propionamides include fenoxanil.

(b17) “Sterol Biosynthesis Inhibitor (SBI): Class III fungicides (FRACcode 17) inhibit 3-ketoreductase during C4-demethylation in sterolproduction. SBI: Class III inhibitors include hydroxyanilide fungicidesand amino-pyrazolinone fungicides. Hydroxyanilides include fenhexamid.Amino-pyrazolinones include fenpyrazamine (S-2-propen-1-yl5-amino-2,3-dihydro-2-(1-methylethyl)-4-(2-methylphenyl)-3-oxo-1H-pyrazole-1-carbothioate).

(b18) “Squalene-epoxidase inhibitor fungicides” (FRAC code 18) (SBI:Class IV) inhibit squalene-epoxidase in the sterol biosynthesis pathway.Sterols such as ergosterol are needed for membrane structure andfunction, making them essential for the development of functional cellwalls. Therefore exposure to these fungicides results in abnormal growthand eventually death of sensitive fungi. Squalene-epoxidase inhibitorfungicides include thiocarbamate and allylamine fungicides. Thethiocarbamates include pyributicarb. The allylamines include naftifineand terbinafine.

(b19) “Polyoxin fungicides” (FRAC code 19) inhibit chitin synthase.Examples include polyoxin.

(b20) “Phenylurea fungicides” (FRAC code 20) are proposed to affect celldivision. Examples include pencycuron.

(b21) “Quinone inside inhibitor (QiI) fungicides” (FRAC code 21) inhibitComplex III mitochondrial respiration in fungi by affecting ubiquinonereductase. Reduction of ubiquinone is blocked at the “quinone inside”(Q_(i)) site of the cytochrome bc₁ complex, which is located in theinner mitochondrial membrane of fungi. Inhibiting mitochondrialrespiration prevents normal fungal growth and development. Quinoneinside inhibitor fungicides include cyanoimidazole and sulfamoyltriazolefungicides. The cyanoimidazoles include cyazofamid. Thesulfamoyltriazoles include amisulbrom.

(b22) “Benzamide and thiazole carboxamide fungicides” (FRAC code 22)inhibit mitosis by binding to β-tubulin and disrupting microtubuleassembly. Inhibition of microtubule assembly can disrupt cell division,transport within the cell and cell structure. The benzamides includezoxamide. The thiazole carboxamides include ethaboxam.

(b23) “Enopyranuronic acid antibiotic fungicides” (FRAC code 23) inhibitgrowth of fungi by affecting protein biosynthesis. Examples includeblasticidin-S.

(b24) “Hexopyranosyl antibiotic fungicides” (FRAC code 24) inhibitgrowth of fungi by affecting protein biosynthesis. Examples includekasugamycin.

(b25) “Glucopyranosyl antibiotic: protein synthesis fungicides” (FRACcode 25) inhibit growth of fungi by affecting protein biosynthesis.Examples include streptomycin.

(b26) “Glucopyranosyl antibiotic: trehalase and inositol biosynthesisfungicides” (FRAC code 26) inhibit trehalase and inositol biosynthesis.Examples include validamycin.

(b27) “Cyanoacetamideoxime fungicides (FRAC code 27) include cymoxanil.

(b28) “Carbamate fungicides” (FRAC code 28) are considered multi-siteinhibitors of fungal growth. They are proposed to interfere with thesynthesis of fatty acids in cell membranes, which then disrupts cellmembrane permeability. Propamacarb, iodocarb, and prothiocarb areexamples of this fungicide class.

(b29) “Oxidative phosphorylation uncoupling fungicides” (FRAC code 29)inhibit fungal respiration by uncoupling oxidative phosphorylation.Inhibiting respiration prevents normal fungal growth and development.This class includes 2,6-dinitroanilines such as fluazinam, anddinitrophenyl crotonates such as dinocap, meptyldinocap and binapacryl.

(b30) “Organo tin fungicides” (FRAC code 30) inhibit adenosinetriphosphate (ATP) synthase in oxidative phosphorylation pathway.Examples include fentin acetate, fentin chloride and fentin hydroxide.

(b31) “Carboxylic acid fungicides” (FRAC code 31) inhibit growth offungi by affecting deoxyribonucleic acid (DNA) topoisomerase type II(gyrase). Examples include oxolinic acid.

(b32) “Heteroaromatic fungicides” (Fungicide Resistance Action Committee(FRAC) code 32) are proposed to affect DNA/ribonucleic acid (RNA)synthesis. Heteroaromatic fungicides include isoxazoles andisothiazolones. The isoxazoles include hymexazole and the isothiazolonesinclude octhilinone.

(b33) “Phosphonate fungicides” (FRAC code 33) include phosphorous acidand its various salts, including fosetyl-aluminum.

(b34) “Phthalamic acid fungicides” (FRAC code 34) include teclofthalam.

(b35) “Benzotriazine fungicides” (FRAC code 35) include triazoxide.

(b36) “Benzene-sulfonamide fungicides” (FRAC code 36) includeflusulfamide.

(b37) “Pyridazinone fungicides” (FRAC code 37) include diclomezine.

(b38) “Thiophene-carboxamide fungicides” (FRAC code 38) are proposed toaffect ATP production. Examples include silthiofam.

(b39) “Complex I NADH oxidoreductase inhibitor fungicides” (FRAC code39) inhibit electron transport in mitochondria and includepyrimidinamines such as diflumetorim, and pyrazole-5-carboxamides suchas tolfenpyrad.

(b40) “Carboxylic acid amide (CAA) fungicides” (FRAC code 40) inhibitcellulose synthase which prevents growth and leads to death of thetarget fungus. Carboxylic acid amide fungicides include cinnamic acidamide, valinamide and other carbamate, and mandelic acid amidefungicides. The cinnamic acid amides include dimethomorph, flumorph andpyrimorph(3-(2-chloro-4-pyridinyl)-3-[4-(1,1-dimethylethyl)phenyl]-1-(4-morpholinyl)-2-propene-1-one).The valinamide and other carbamates include benthiavalicarb,benthiavalicarb-isopropyl, iprovalicarb, tolprocarb(2,2,2-trifluoroethylN-[(1S)-2-methyl-1-[[(4-methylbenzoyl)amino]methyl]propyl]carbamate) andvalifenalate(methylN-[(1-methylethoxy)carbonyl]-L-valyl-3-(4-chlorophenyl)-β-alaninate)(also known as valiphenal). The mandelic acid amides includemandipropamid,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(methylsulfonyl)-amino]butanamideandN-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]-ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide.

(b41) “Tetracycline antibiotic fungicides” (FRAC code 41) inhibit growthof fungi by affecting protein synthesis. Examples includeoxytetracycline.

(b42) “Thiocarbamate fungicides” (FRAC code 42) include methasulfocarb.

(b43) “Benzamide fungicides” (FRAC code 43) inhibit growth of fungi bydelocalization of spectrin-like proteins. Examples includepyridinylmethyl benzamide fungicides such as fluopicolide (now FRAC code7, pyridinylethyl benzamides).

(b44) “Microbial fungicides” (FRAC code 44) disrupt fungal pathogen cellmembranes. Microbial fungicides include Bacillus species such asBacillus amyloliquefaciens strains QST 713, FZB24, MB1600, D747 and thefungicidal lipopeptides which they produce.

(b45) “Q_(X)I fungicides” (FRAC code 45) inhibit Complex IIImitochondrial respiration in fungi by affecting ubiquinone reductase atan unknown (Q_(X)) site of the cytochrome bc₁ complex. Inhibitingmitochondrial respiration prevents normal fungal growth and development.Q_(X)I fungicides include triazolopyrimidylamines such as ametoctradin(5-ethyl-6-octyl[1,2,4]triazolo[1,5-a]pyrimidin-7-amine).

(b46) “Plant extract fungicides” are proposed to act by cell membranedisruption. Plant extract fungicides include terpene hydrocarbons andterpene alcohols such as the extract from Melaleuca alternifolia (teatree).

(b47) “Host plant defense induction fungicides” (FRAC code P) inducehost plant defense mechanisms. Host plant defense induction fungicidesinclude benzothiadiazoles, benzisothiazole and thiadiazole-carboxamidefungicides. The benzothiadiazoles include acibenzolar-S-methyl. Thebenzisothiazoles include probenazole. The thiadiazole-carboxamidesinclude tiadinil and isotianil.

(b48) “Multi-site contact fungicides” inhibit fungal growth throughmultiple sites of action and have contact/preventive activity. Thisclass of fungicides includes: (b48.1) “copper fungicides” (FRAC codeM1)”, (b48.2) “sulfur fungicides” (FRAC code M2), (b48.3)“dithiocarbamate fungicides” (FRAC code M3), (b48.4) “phthalimidefungicides” (FRAC code M4), (b48.5) “chloronitrile fungicides” (FRACcode M5), (b48.6) “sulfamide fungicides” (FRAC code M6), (b48.7)multi-site contact “guanidine fungicides” (FRAC code M7), (b48.8)“triazine fungicides” (FRAC code M8), (b48.9) “quinone fungicides” (FRACcode M9), (b48.10) “quinoxaline fungicides” (FRAC code M10) and (b48.11)“maleimide fungicides” (FRAC code M11). “Copper fungicides” areinorganic compounds containing copper, typically in the copper(II)oxidation state; examples include copper oxychloride, copper sulfate andcopper hydroxide, including compositions such as Bordeaux mixture(tribasic copper sulfate). “Sulfur fungicides” are inorganic chemicalscontaining rings or chains of sulfur atoms; examples include elementalsulfur. “Dithiocarbamate fungicides” contain a dithiocarbamate molecularmoiety; examples include mancozeb, metiram, propineb, ferbam, maneb,thiram, zineb and ziram. “Phthalimide fungicides” contain a phthalimidemolecular moiety; examples include folpet, captan and captafol.“Chloronitrile fungicides” contain an aromatic ring substituted withchloro and cyano; examples include chlorothalonil. “Sulfamidefungicides” include dichlofluanid and tolyfluanid. Multi-site contact“guanidine fungicides” include, guazatine, iminoctadine albesilate andiminoctadine triacetate. “Triazine fungicides” include anilazine.“Quinone fungicides” include dithianon. “Quinoxaline fungicides” includequinomethionate (also known as chinomethionate). “Maleimide fungicides”include fluoroimide.

(b49) “Fungicides other than fungicides of classes (b1) through (b48)”include certain fungicides whose mode of action may be unknown. Theseinclude: (b49.1) “phenyl-acetamide fungicides” (FRAC code U6), (b49.2)“aryl-phenyl-ketone fungicides” (FRAC code U8), (b49.3) “guanidinefungicides” (FRAC code U12), (b49.4) “thiazolidine fungicides” (FRACcode U13), (b49.5) “pyrimidinone-hydrazone fungicides” (FRAC code U14)and (b49.6) compounds that bind to oxysterol-binding protein asdescribed in PCT Patent Publication WO 2013/009971. Thephenyl-acetamides include cyflufenamid andN-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]-methylene]-benzeneacetamide.The aryl-phenyl ketones include benzophenones such as metrafenone, andbenzoylpyridines such as pyriofenone((5-chloro-2-methoxy-4-methyl-3-pyridinyl)(2,3,4-trimethoxy-6-methylphenyl)methanone).The guanidines include dodine. The thiazolidines include flutianil((2Z)-2-[[2-fluoro-5-(trifluoromethyl)phenyl]thio]-2-[3-(2-methoxyphenyl)-2-thiazolidinylidene]acetonitrile).The pyrimidinone-hydrazones include ferimzone. The (b49.6) classincludes oxathiapiprolin(1-[4-[4-[5-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone)and its R-enantiomer which is1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone(Registry Number 1003319-79-6).

The (b49) class also includes bethoxazin, flometoquin(2-ethyl-3,7-dimethyl-6-[4-(trifluoromethoxy)phenoxy]-4-quinolinylmethyl carbonate), fluoroimide, neo-asozin (ferric methanearsonate),picarbutrazox (1,1-dimethylethylN-[6-[[[[((Z)-1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate),pyrrolnitrin, quinomethionate, tebufloquin(6-(1,1-dimethylethyl)-8-fluoro-2,3-dimethyl-4-quinolinyl acetate),tolnifanide(N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide),2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-butyn-1-ylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate,(N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide),N-[4-[4-chloro-3-(trifluoromethyl)-phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,N-[[(cyclopropyl-methoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide,2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone,5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine,5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine and 4-fluorophenylN-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]-propyl]carbamate, pentylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenyl-methylene]amino]oxy]methyl]-2-pyridinyl]carbamate,pentylN-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamateand pentylN-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]-carbamate.The (b49) class further includes mitosis- and cell division-inhibitingfungicides besides those of the particular classes described above(e.g., (b1), (b10) and (b22)).

Additional “Fungicides other than fungicides of classes (b1) through(b48)” whose mode of action may be unknown, or may not yet be classifiedinclude a fungicidal compound selected from components (b49.7) through(b49.12), as shown below.

Component (b49.7) relates to a compound of Formula b49.7

-   -   wherein R^(b1) is

Examples of a compound of Formula b49.7 include (b49.7a)(2-chloro-6-fluorophenyl)-methyl2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazole-carboxylate(Registry Number 1299409-40-7) and (b49.7b)(1R)-1,2,3,4-tetrahydro-1-naphthalenyl2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate(Registry Number 1299409-42-9). Methods for preparing compounds ofFormula b49.7 are described in PCT Patent Publications WO 2009/132785and WO 2011/051243.

Component (b49.8) relates to a compound of Formula b49.8

wherein R^(b2) is CH₃, CF₃ or CHF₂; R^(b3) is CH₃, CF₃ or CHF₂; R^(b4)is halogen or

-   -   cyano; and n is 0, 1, 2 or 3.

Examples of a compound of Formula b49.8 include (b49.8a)1-[4-[4-[5-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone.Methods for preparing compounds of Formula b49.8 are described in PCTPatent Application PCT/US11/64324.

Component (b49.9) relates to a compound of Formula b49.9

wherein R^(b5) is —CH₂OC(O)CH(CH₃)₂, —C(O)CH₃, —CH₂OC(O)CH₃,—C(O)OCH₂CH(CH₃)₂ or

Examples of a compound of Formula b49.9 include (b49.9a)[[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]amino]carbonyl]-3-pyridinyl]oxy]methyl2-methylpropanoate (Registry Number 517875-34-2), (b49.9b)(3S,6S,7R,8R)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]-carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methyl-propanoate (Registry Number 234112-93-7), (b49.9c)(3S,6S,7R,8R)-3-[[[3-[(acetyloxy)methoxy]-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate (Registry Number 517875-31-9), (b49.9d)(3S,6S,7R,8R)-3-[[[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridinyl]-carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate (Registry Number 328256-72-0), and (b49.9e)N-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-2-pyridinyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)-L-arabinonoyl]-L-serine,(1→4′)-lactone (Registry Number 1285706-70-8). Methods for preparingcompounds of Formula b49.9 are described in PCT Patent Publications WO99/40081, WO 2001/014339, WO 2003/035617 and WO 2011044213.

Component (b49.10) relates to a compound of Formula b49.10

wherein R^(b6) is H or F, and R^(b7) is —CF₂CHFCF₃ or —CF₂CF₂H. Examplesof a compound of Formula b49.10 are (b49.10a)3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexafluoro-propoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide(Registry Number 1172611-40-3) and (b49.10b)3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide(Registry Number 923953-98-4). Compounds of Formula 49.10 can beprepared by methods described in PCT Patent Publication WO 2007/017450.

Component b49.11 relates a compound of Formula b49.11

wherein

-   -   R^(b8) is halogen, C₁-C₄ alkoxy or C₂-C₄ alkynyl;    -   R^(b9) is H, halogen or C₁-C₄ alkyl;    -   R^(b10) is C₁-C₁₂ alkyl, C₁-C₁₂ haloalkyl, C₁-C₁₂ alkoxy, C₂-C₁₂        alkoxyalkyl, C₂-C₁₂ alkenyl, C₂-C₁₂ alkynyl, C₄-C₁₂        alkoxyalkenyl, C₄-C₁₂ alkoxyalkynyl, C₁-C₁₂ alkylthio or C₂-C₁₂        alkylthioalkyl;    -   R^(b11) is methyl or —Y^(b13)—R^(b12);    -   R^(b12) is C₁-C₂ alkyl; and    -   Y^(b13) is CH₂, O or S.

Examples of compounds of Formula b49.11 include (b49.11a)2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide,(b49.11b)2-[(3-ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)-acetamide,(b49.11c)N-(1,1-dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide,(b49.11d)2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propyn-1-yl)-2-(methylthio)acetamideand (b49.11e)2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)butanamide. Compoundsof Formula b49.11, their use as fungicides and methods of preparationare generally known; see, for example, PCT Patent Publications WO2004/047538, WO 2004/108663, WO 2006/058699, WO 2006/058700, WO2008/110355, WO 2009/030469, WO 2009/049716 and WO 2009/087098.

Component (b49.12) relates toN′-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methylmethanimidamide,which is believed to inhibit C24-methyl transferase involved in thebiosynthesis of sterols.

Therefore of note is a mixture (i.e. composition) comprising a compoundof Formula 1 and at least one fungicidal compound selected from thegroup consisting of the aforedescribed classes (b1) through (b49). Alsoof note is a composition comprising said mixture (in fungicidallyeffective amount) and further comprising at least one additionalcomponent selected from the group consisting of surfactants, soliddiluents and liquid diluents. Of particular note is a mixture (i.e.composition) comprising a compound of Formula 1 and at least onefungicidal compound selected from the group of specific compounds listedabove in connection with classes (b1) through (b49). Also of particularnote is a composition comprising said mixture (in fungicidally effectiveamount) and further comprising at least one additional surfactantselected from the group consisting of surfactants, solid diluents andliquid diluents.

Examples of component (b) fungicides include acibenzolar-S-methyl,aldimorph, ametoctradin, amisulbrom, anilazine, azaconazole,azoxystrobin, benalaxyl (including benalaxyl-M), benodanil, benomyl,benthiavalicarb (including benthiavalicarb-isopropyl), benzovindiflupyr,bethoxazin, binapacryl, biphenyl, bitertanol, bixafen, blasticidin-S,boscalid, bromuconazole, bupirimate, buthiobate, captafol, captan,carbendazim, carboxin, carpropamid, chloroneb, chlorothalonil,chlozolinate, clotrimazole, copper hydroxide, copper oxychloride, coppersulfate, coumoxystrobin, cyazofamid, cyflufenamid, cymoxanil,cyproconazole, cyprodinil, dichlofluanid, diclocymet, diclomezine,dicloran, diethofencarb, difenoconazole, diflumetorim, dimethirimol,dimethomorph, dimoxystrobin, diniconazole (including diniconazole-M),dinocap, dithianon, dithiolanes, dodemorph, dodine, econazole,edifenphos, enoxastrobin (also known as enestroburin), epoxiconazole,etaconazole, ethaboxam, ethirimol, etridiazole, famoxadone, fenamidone,fenarimol, fenaminstrobin, fenbuconazole, fenfuram, fenhexamid,fenoxanil, fenpiclonil, fenpropidin, fenpropimorph, fenpyrazamine,fentin acetate, fentin chloride, fentin hydroxide, ferbam, ferimzone,flometoquin, fluazinam, fludioxonil, flufenoxystrobin, flumorph,fluopicolide, fluopyram, flouroimide, fluoxastrobin, fluquinconazole,flusilazole, flusulfamide, flutianil, flutolanil, flutriafol,fluxapyroxad, folpet, fthalide, fuberidazole, furalaxyl, furametpyr,guazatine, hexaconazole, hymexazole, imazalil, imibenconazole,iminoctadine albesilate, iminoctadine triacetate, iodocarb, ipconazole,iprobenfos, iprodione, iprovalicarb, isoconazole, isofetamid,isoprothiolane, isopyrazam, isotianil, kasugamycin, kresoxim-methyl,mancozeb, mandepropamid, mandestrobin, maneb, mepanipyrim, mepronil,meptyldinocap, metalaxyl (including metalaxyl-M/mefenoxam), metconazole,methasulfocarb, metiram, metominostrobin, metrafenone, miconazole,myclobutanil, naftifine, neo-asozin, nuarimol, octhilinone, ofurace,orysastrobin, oxadixyl, oxathiapiprolin, oxolinic acid, oxpoconazole,oxycarboxin, oxytetracycline, pefurazoate, penconazole, pencycuron,penflufen, penthiopyrad, phosphorous acid (including salts thereof,e.g., fosetyl-aluminum), picarbutrazox, picoxystrobin, piperalin,polyoxin, probenazole, prochloraz, procymidone, propamacarb,propiconazole, propineb, proquinazid, prothiocarb, prothioconazole,pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrazophos,pyribencarb, pyributicarb, pyrifenox, pyrimethanil, pyriofenone,pyrisoxazole, pyroquilon, pyrrolnitrin, quinconazole, quinomethionate,quinoxyfen, quintozene, sedaxane, silthiofam, simeconazole, spiroxamine,streptomycin, sulfur, tebuconazole, tebufloquin, teclofthalam,tecnazene, terbinafine, tetraconazole, thiabendazole, thifluzamide,thiophanate, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl,tolnifanide, tolprocarb, tolyfluanid, triadimefon, triadimenol,triarimol, triticonazole, triazoxide, tribasic copper sulfate,tricyclazole, triclopyricarb, tridemorph, trifloxystrobin, triflumizole,triforine, trimorphamide, uniconazole, uniconazole-P, validamycin,valifenalate (also known as valiphenal), vinclozolin, zineb, ziram,zoxamide,(3S,6S,7R,8R)-3-[[[3-[(acetyloxy)methoxy]-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate,(3S,6S,7R,8R)-3-[[[3-(acetyloxy)-4-methoxy-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate,N-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxy-2-pyridinyl]carbonyl]-O-[2,5-dideoxy-3-O-(2-methyl-1-oxopropyl)-2-(phenylmethyl)-L-arabinonoyl]-L-serine,(1→4′)-lactone,N-[2-(1S,2R)-[1,1′-bicyclopropyl]-2-ylphenyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-butyn-1-yl)-2-(methylthio)acetamide,2-[(3-bromo-6-quinolinyl)oxy]-N-(1,1-dimethylethyl)butanamide,2-[(3-bromo-8-methyl-6-quinolinyl)oxy]-N-(1,1-dimethyl-2-propyn-1-yl)-2-(methylthio)acetamide,2-butoxy-6-iodo-3-propyl-4H-1-benzopyran-4-one, 3-butyn-1-ylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)-phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate,α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol,2-[2-(1-chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,(αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol,rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1H-1,2,4-triazole,rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole,3-[5-(4-chlorophenyl)-2,3-dimethyl-3-isoxazolidinyl]pyridine,(2-chloro-6-fluorophenyl)methyl2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate,N′-[4-[[3-[(4-chlorophenyl)methyl]-1,2,4-thiadiazol-5-yl]oxy]-2,5-dimethylphenyl]-N-ethyl-N-methyl-methanimidamide,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]-ethyl]-3-methyl-2-[(methylsulfonyl)amino]butanamide,N-[2-[4-[[3-(4-chlorophenyl)-2-propyn-1-yl]oxy]-3-methoxyphenyl]ethyl]-3-methyl-2-[(ethylsulfonyl)amino]butanamide,N′-[4-[4-chloro-3-(trifluoromethyl)phenoxy]-2,5-dimethylphenyl]-N-ethyl-N-methyl-methanimidamide,N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[2-(1-methyl-ethyl)phenyl]methyl]-1H-pyrazole-4-carboxamide,N-[[(cyclopropylmethoxy)amino][6-(difluoromethoxy)-2,3-difluorophenyl]methylene]benzeneacetamide,N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,N-(3′,4′-difluoro[1,1′-biphenyl]-2-yl)-3-(trifluoromethyl)-2-pyrazinecarboxamide,3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide,3-(difluoromethyl)-N-[4-fluoro-2-(1,1,2,3,3,3-hexa-fluoropropoxy)phenyl]-1-methyl-1H-pyrazole-4-carboxamide,5,8-difluoro-N-[2-[3-methoxy-4-[[4-(trifluoromethyl)-2-pyridinyl]oxy]phenyl]ethyl]-4-quinazolinamine,3-(difluoromethyl)-1-methyl-N-[2-(1,1,2,2-tetrafluoroethoxy)phenyl]-1H-pyrazole-4-carboxamide,1-[4-[4-[5R-[(2,6-difluorophenoxy)methyl]-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperdinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,N-(1,1-dimethyl-2-butyn-1-yl)-2-[(3-ethynyl-6-quinolinyl)oxy]-2-(methylthio)acetamide,2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone,2-[(3-ethynyl-6-quinolinyl)oxy]-N-[1-(hydroxymethyl)-1-methyl-2-propyn-1-yl]-2-(methylthio)acetamide,4-fluorophenylN-[1-[[[1-(4-cyanophenyl)ethyl]sulfonyl]methyl]propyl]carbamate,5-fluoro-2-[(4-fluorophenyl)methoxy]-4-pyrimidinamine,5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidinamine,(3S,6S,7R,8R)-3-[[[4-methoxy-3-[[(2-methylpropoxy)carbonyl]oxy]-2-pyridinyl]carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxonan-7-yl2-methylpropanoate,α-(methoxyimino)-N-methyl-2-[[[1-[3-(trifluoro-methyl)phenyl]ethoxy]imino]methyl]benzeneacetamide,[[4-methoxy-2-[[[(3S,7R,8R,9S)-9-methyl-8-(2-methyl-1-oxopropoxy)-2,6-dioxo-7-(phenylmethyl)-1,5-dioxonan-3-yl]-amino]carbonyl]-3-pyridinyl]oxy]methyl2-methylpropanoate, pentylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate,pentylN-[4-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-thiazolyl]carbamate,and pentylN-[6-[[[[(Z)-(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamateand (1R)-1,2,3,4-tetrahydro-1-naphthalenyl2-[1-[2-[3,5-bis(difluoromethyl)-1H-pyrazol-1-yl]acetyl]-4-piperidinyl]-4-thiazolecarboxylate.Therefore of note is a fungicidal composition comprising as component(a) a compound of Formula 1 (or an N-oxide or salt thereof) and ascomponent (b) at least one fungicide selected from the preceding list.

Of particular note are combinations of compounds of Formula 1 (or anN-oxide or salt thereof) (i.e. Component (a) in compositions) withazoxystrobin, benzovindiflupyr, bixafen, captan, carpropamid,chlorothalonil, copper hydroxide, copper oxychloride, copper sulfate,cymoxanil, cyproconazole, cyprodinil, diethofencarb, difenoconazole,dimethomorph, epoxiconazole, ethaboxam, fenarimol, fenhexamid,fluazinam, fludioxonil, fluopyram, flusilazole, flutianil, flutriafol,fluxapyroxad, folpet, iprodione, isofetamid, isopyrazam,kresoxim-methyl, mancozeb, mandestrobin, meptyldinocap, metalaxyl(including metalaxyl-M/mefenoxam), metconazole, metrafenone,myclobutanil, oxathiapiprolin, penflufen, penthiopyrad, phosphorous acid(including salts thereof, e.g., fosetyl-aluminum), picoxystrobin,propiconazole, proquinazid, prothioconazole, pyraclostrobin,pyrimethanil, sedaxane spiroxamine, sulfur, tebuconazole,thiophanate-methyl, trifloxystrobin, zoxamide,α-(1-chlorocyclopropyl)-α-[2-(2,2-dichlorocyclopropyl)ethyl]-1H-1,2,4-triazole-1-ethanol,2-[2-(1chlorocyclopropyl)-4-(2,2-dichlorocyclopropyl)-2-hydroxybutyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,N-[2-(2,4-dichlorophenyl)-2-methoxy-1-methylethyl]-3-(difluoromethyl)-1-methyl-1H-pyrazole-4-carboxamide,3-(difluoromethyl)-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-1-methyl-1H-pyrazole-4-carboxamide,1-[4-[4-[5R-(2,6-difluorophenyl)-4,5-dihydro-3-isoxazolyl]-2-thiazolyl]-1-piperidinyl]-2-[5-methyl-3-(trifluoromethyl)-1H-pyrazol-1-yl]ethanone,1,1-dimethylethylN-[6-[[[[(1-methyl-1H-tetrazol-5-yl)phenylmethylene]amino]oxy]methyl]-2-pyridinyl]carbamate,2,6-dimethyl-1H,5H-[1,4]dithiino[2,3-c:5,6-c′]dipyrrole-1,3,5,7(2H,6H)-tetrone,5-fluoro-2-[(4-fluoro-phenyl)methoxy]-4-pyrimidinamine,5-fluoro-2-[(4-methylphenyl)methoxy]-4-pyrimidin-amine,(αS)-[3-(4-chloro-2-fluorophenyl)-5-(2,4-difluorophenyl)-4-isoxazolyl]-3-pyridinemethanol,rel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]-methyl]-1H-1,2,4-triazole,rel-2-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-1,2-dihydro-3H-1,2,4-triazole-3-thione,andrel-1-[[(2R,3S)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-2-oxiranyl]methyl]-5-(2-propen-1-ylthio)-1H-1,2,4-triazole(i.e. as Component (b) in compositions).

Preferred for better control of plant diseases caused by fungal plantpathogens (e.g., lower use rate or broader spectrum of plant pathogenscontrolled) or resistance management are mixtures of a compound of thisinvention with a fungicide selected from the group.

Examples of other biologically active compounds or agents with whichcompounds of this invention can be formulated are: invertebrate pestcontrol compounds or agents such as abamectin, acephate, acetamiprid,acrinathrin, afidopyropen([(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-3-[(cyclopropylcarbonyl)oxy]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-6,12-dihydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-4-yl]methylcyclopropanecarboxylate), amidoflumet (S-1955), avermectin,azadirachtin, azinphos-methyl, bifenthrin, bifenazate, buprofezin,carbofuran, cartap, chlorantraniliprole, chlorfenapyr, chlorfluazuron,chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin,cyantraniliprole(3-bromo-1-(3-chloro-2-pyridinyl)-N-[4-cyano-2-methyl-6-[(methylamino)carbonyl]phenyl]-1H-pyrazole-5-carboxamide),cyclaniliprole(3-bromo-N-[2-bromo-4-chloro-6-[[(1-cyclopropylethyl)amino]carbonyl]phenyl]-1-(3-chloro-2-pyridinyl)-1H-pyrazole-5-carboxamide),cycloxaprid((5S,8R)-1-[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-5,8-epoxy-1H-imidazo[1,2-a]azepine),cyflumetofen, cyfluthrin, beta-cyfluthrin, cyhalothrin,lambda-cyhalothrin, cypermethrin, cyromazine, deltamethrin,diafenthiuron, diazinon, dieldrin, diflubenzuron, dimefluthrin,dimethoate, dinotefuran, diofenolan, emamectin, endosulfan,esfenvalerate, ethiprole, fenothiocarb, fenoxycarb, fenpropathrin,fenvalerate, fipronil, flonicamid, flubendiamide, flucythrinate,flufenoxystrobin(methyl(αE)-2-[[2-chloro-4-(trifluoromethyl)phenoxy]methyl]-α-(methoxymethylene)benzeneacetate),flufensulfone(5-chloro-2-[(3,4,4-trifluoro-3-buten-1-yl)sulfonyl]thiazole),flupiprole(1-[2,6-dichloro-4-(trifluoromethyl)phenyl]-5-[(2-methyl-2-propen-1-yl)amino]-4-[(trifluoromethyl)sulfinyl]-1H-pyrazole-3-carbonitrile),flupyradifurone(4-[[(6-chloro-3-pyridinyl)methyl](2,2-difluoroethyl)amino]-2(5H)-furanone),tau-fluvalinate, flufenerim (UR-50701), flufenoxuron, fonophos,halofenozide, heptafluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl2,2-dimethyl-3-[(1Z)-3,3,3-trifluoro-1-propen-1-yl]cyclopropanecarboxylate),hexaflumuron, hydramethylnon, imidacloprid, indoxacarb, isofenphos,lufenuron, malathion, meperfluthrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate),metaflumizone, metaldehyde, methamidophos, methidathion, methomyl,methoprene, methoxychlor, methoxyfenozide, metofluthrin, milbemycinoxime, momfluorothrin([2,3,5,6-tetrafluoro-4-(methoxymethyl)phenyl]methyl3-(2-cyano-1-propen-1-yl)-2,2-dimethylcyclopropanecarboxylate),monocrotophos, nicotine, nitenpyram, nithiazine, novaluron, noviflumuron(XDE-007), oxamyl, pyflubumide(1,3,5-trimethyl-N-(2-methyl-1-oxopropyl)-N-[3-(2-methylpropyl)-4-[2,2,2-trifluoro-1-methoxy-1-(trifluoromethyl)ethyl]phenyl]-1H-pyrazole-4-carboxamide),parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet,phosphamidon, pirimicarb, profenofos, profluthrin, pymetrozine,pyrafluprole, pyrethrin, pyridalyl, pyrifluquinazon,pyriminostrobin(methyl(αE)-2-[[[2-[(2,4-dichlorophenyl)amino]-6-(trifluoromethyl)-4-pyrimidinyl]oxy]methyl]-α-(methoxymethylene)benzeneacetate),pyriprole, pyriproxyfen, rotenone, ryanodine, spinetoram, spinosad,spirodiclofen, spiromesifen (BSN 2060), spirotetramat, sulfoxaflor,sulprofos, tebufenozide, teflubenzuron, tefluthrin, terbufos,tetrachlorvinphos, tetramethylfluthrin, thiacloprid, thiamethoxam,thiodicarb, thiosultap-sodium, tolfenpyrad, tralomethrin, triazamate,trichlorfon and triflumuron; and biological agents includingentomopathogenic bacteria, such as Bacillus thuringiensis subsp.aizawai, Bacillus thuringiensis subsp. kurstaki, and the encapsulateddelta-endotoxins of Bacillus thuringiensis (e.g., Cellcap, MPV, MPVII);entomopathogenic fungi, such as green muscardine fungus; andentomopathogenic virus including baculovirus, nucleopolyhedro virus(NPV) such as HzNPV, AfNPV; and granulosis virus (GV) such as CpGV.

Compounds of this invention and compositions thereof can be applied toplants genetically transformed to express proteins toxic to invertebratepests (such as Bacillus thuringiensis delta-endotoxins). The effect ofthe exogenously applied fungicidal compounds of this invention may besynergistic with the expressed toxin proteins.

General references for agricultural protectants (i.e. insecticides,fungicides, nematocides, acaricides, herbicides and biological agents)include The Pesticide Manual, 13th Edition, C. D. S. Tomlin, Ed.,British Crop Protection Council, Farnham, Surrey, U.K., 2003 and TheBioPesticide Manual, 2nd Edition, L. G. Copping, Ed., British CropProtection Council, Farnham, Surrey, U. K., 2001.

For embodiments where one or more of these various mixing partners areused, the weight ratio of these various mixing partners (in total) tothe compound of Formula 1 is typically between about 1:3000 and about3000:1. Of note are weight ratios between about 1:300 and about 300:1(for example ratios between about 1:30 and about 30:1). One skilled inthe art can easily determine through simple experimentation thebiologically effective amounts of active ingredients necessary for thedesired spectrum of biological activity. It will be evident thatincluding these additional components may expand the spectrum ofdiseases controlled beyond the spectrum controlled by the compound ofFormula 1 alone.

In certain instances, combinations of a compound of this invention withother biologically active (particularly fungicidal) compounds or agents(i.e. active ingredients) can result in a greater-than-additive (i.e.synergistic) effect. Reducing the quantity of active ingredientsreleased in the environment while ensuring effective pest control isalways desirable. When synergism of fungicidal active ingredients occursat application rates giving agronomically satisfactory levels of fungalcontrol, such combinations can be advantageous for reducing cropproduction cost and decreasing environmental load.

Also in certain instances, combinations of a compound of the inventionwith other biologically active compounds or agents can result in aless-than-additive (i.e. safening) effect on organisms beneficial to theagronomic environment. For example, a compound of the invention maysafen a herbicide on crop plants or protect a beneficial insect species(e.g., insect predators, pollinators such as bees) from an insecticide.

Fungicides of note for formulation with compounds of Formula 1 toprovide mixtures useful in seed treatment include but are not limited toamisulbrom, azoxystrobin, boscalid, carbendazim, carboxin, cymoxanil,cyproconazole, difenoconazole, dimethomorph, fluazinam, fludioxonil,flufenoxystrobin, fluquinconazole, fluopicolide, fluoxastrobin,flutriafol, fluxapyroxad, ipconazole, iprodione, metalaxyl, mefenoxam,metconazole, myclobutanil, paclobutrazole, penflufen, picoxystrobin,prothioconazole, pyraclostrobin, sedaxane, silthiofam, tebuconazole,thiabendazole, thiophanate-methyl, thiram, trifloxystrobin andtriticonazole.

Invertebrate pest control compounds or agents with which compounds ofFormula 1 can be formulated to provide mixtures useful in seed treatmentinclude but are not limited to abamectin, acetamiprid, acrinathrin,afidopyropen, amitraz, avermectin, azadirachtin, bensultap, bifenthrin,buprofezin, cadusafos, carbaryl, carbofuran, cartap,chlorantraniliprole, chlorfenapyr, chlorpyrifos, clothianidin,cyantraniliprole, cyclaniliprole, cyfluthrin, beta-cyfluthrin,cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin,alpha-cypermethrin, zeta-cypermethrin, cyromazine, deltamethrin,dieldrin, dinotefuran, diofenolan, emamectin, endosulfan, esfenvalerate,ethiprole, etofenprox, etoxazole, fenothiocarb, fenoxycarb, fenvalerate,fipronil, flonicamid, flubendiamide, fluensulfone, flufenoxuron,flufiprole, flupyradifurone, fluvalinate, formetanate, fosthiazate,heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, indoxacarb,lufenuron, meperfluthrin, metaflumizone, methiocarb, methomyl,methoprene, methoxyfenozide, momfluorothrin, nitenpyram, nithiazine,novaluron, oxamyl, pyflubumide, pymetrozine, pyrethrin, pyridaben,pyriminostrobin, pyridalyl, pyriproxyfen, ryanodine, spinetoram,spinosad, spirodiclofen, spiromesifen, spirotetramat, sulfoxaflor,tebufenozide, tetramethrin, tetramethylfluthrin, thiacloprid,thiamethoxam, thiodicarb, thiosultap-sodium, tralomethrin, triazamate,triflumuron, Bacillus thuringiensis delta-endotoxins, strains ofBacillus thuringiensis and strains of Nucleo polyhydrosis viruses.

Compositions comprising compounds of Formula 1 useful for seed treatmentcan further comprise bacteria and fungi that have the ability to provideprotection from the harmful effects of plant pathogenic fungi orbacteria and/or soil born animals such as nematodes. Bacteria exhibitingnematicidal properties may include but are not limited to Bacillusfirmus, Bacillus cereus, Bacillius subtiliis and Pasteuria penetrans. Asuitable Bacillus firmus strain is strain CNCM I-1582 (GB-126) which iscommercially available as BioNem™. A suitable Bacillus cereus strain isstrain NCMM I-1592. Both Bacillus strains are disclosed in U.S. Pat. No.6,406,690. Other suitable bacteria exhibiting nematicidal activity areB. amyloliquefaciens IN937a and B. subtilis strain GB03. Bacteriaexhibiting fungicidal properties may include but are not limited to B.pumilus strain GB34. Fungal species exhibiting nematicidal propertiesmay include but are not limited to Myrothecium verrucaria, Paecilomyceslilacinus and Purpureocillium lilacinum.

Seed treatments can also include one or more nematicidal agents ofnatural origin such as the elicitor protein called harpin which isisolated from certain bacterial plant pathogens such as Erwiniaamylovora. An example is the Harpin-N-Tek seed treatment technologyavailable as N-Hibit™ Gold CST.

Seed treatments can also include one or more species of legume-rootnodulating bacteria such as the microsymbiotic nitrogen-fixing bacteriaBradyrhizobium japonicum. These inocculants can optionally include oneor more lipo-chitooligosaccharides (LCOs), which are nodulation (Nod)factors produced by rhizobia bacteria during the initiation of noduleformation on the roots of legumes. For example, the Optimize® brand seedtreatment technology incorporates LCO Promoter Technology™ incombination with an inocculant.

Seed treatments can also include one or more isoflavones which canincrease the level of root colonization by mycorrhizal fungi.Mycorrhizal fungi improve plant growth by enhancing the root uptake ofnutrients such as water, sulfates, nitrates, phosphates and metals.Examples of isoflavones include, but are not limited to, genistein,biochanin A, formononetin, daidzein, glycitein, hesperetin, naringeninand pratensein. Formononetin is available as an active ingredient inmycorrhizal inocculant products such as PHC Colonize® AG.

Seed treatments can also include one or more plant activators thatinduce systemic acquired resistance in plants following contact by apathogen. An example of a plant activator which induces such protectivemechanisms is acibenzolar-S-methyl.

The following Tests demonstrate the control efficacy of compounds ofthis invention on specific pathogens. The pathogen control protectionafforded by the compounds is not limited, however, to these species. SeeIndex Tables A-H for compound descriptions. The following abbreviationsare used in the Tables which follow: Me means methyl, Et means ethyl, Prmeans propyl, i-Pr means isopropyl, i-Pre means isopropenyl, c-Pr meanscyclopropyl, OMe means methoxy, TMS means trimethylsilyl, Ph meansphenyl, MeOC(═O) means methoxycarbonyl and CN means cyano. Where(R³)_(n) is listed as “H”, this means that n is 0 and the ringcomprising G is not substituted with R³. The abbreviation “Ex.” standsfor “Example” and is followed by a number indicating in which examplethe compound is prepared. In the following Index Tables, Mass spectraare reported as the molecular weight of the highest isotopic abundanceparent ion (M+1) formed by addition of H⁺ (molecular weight of 1) to themolecule, or (M−1) formed by the loss of H⁺ (molecular weight of 1) fromthe molecule, observed by using an liquid chromatography coupled to amass spectrometer (MS) using either atmospheric pressure chemicalionization (AP⁺) or electrospray ionization (ESI⁺), where “amu” standsfor atomic mass units. In the following Index Tables A through F, “G” isdefined as the following:

INDEX TABLE A

Cmpd. No. R⁵ R^(2a) G (R³)_(n) Q m.p. (° C.) M + 1 M − 1  1 H CH₃ G-3a H3-CF₃-1H-pyrazol-1-yl * (Ex. 1)  2 H H G-3a H 3-CF₃-1H-pyrazol-1-yl 441 3 F H G-1b H 3-CF₃-1H-pyrazol-1-yl 458  4 H H G-4a H3-CF₃-1H-pyrazol-1-yl 442  5 H H G-4a H 3-Cl-1H-pyrazol-1-yl 408  6 H HG-4a H 4-Cl-1H-pyrazol-1-yl 408  7 H H G-4a H 1H-pyrazol-1-yl 374  8 H HG-4a H 3-phenyl-1H-pyrazol-1-yl 450  9 H H G-1b H3-CF₃-1H-pyrazol-1-yl * (Ex. 2)  10 H H G-1a 2-Cl 4-Br-1H-pyrazol-1-yl** 485  11 H H G-1a 2-Cl 3-CF₃-1H-pyrazol-1-yl 112-115  12 F H G-1a 2-Cl3-CF₃-1H-pyrazol-1-yl * 492 (Ex. 3)  13 H H G-1b 6-NO₂3-CF₃-1H-pyrazol-1-yl 485  14 H H G-1b 6-OCH₃ 3-CF₃-1H-pyrazol-1-yl 471 16 H H G-4a 3-Br 3-CF₃-1H-pyrazol-1-yl 150-153 521  17 H CH₃ G-4a 3-Cl3-CF₃-1H-pyrazol-1-yl 489  18 F CH₃ G-4a 3-Cl 3-CF₃-1H-pyrazol-1-yl 510 19 H CH₃ G-1a 2-Cl 3-CF₃-1H-pyrazol-1-yl 489  20 H H G-1a 2-Cl4-Cl-1H-pyrazol-1-yl 441  21 H CH₃ G-1b 4-CF₃ 3-CF₃-1H-pyrazol-1-yl 522 22 H CH₃ G-1b 5-Cl 3-CF₃-1H-pyrazol-1-yl 488  23 F H G-1a 2-OCF₃3-CF₃-1H-pyrazol-1-yl 94-96  24 H H G-1a 2,6-di-Cl 1H-pyrazol-1-yl133-136  25 F H G-1a 2-OMe 3-CF₃-1H-pyrazol-1-yl 126-129  26 H CH₃ G-1b4-Me 3-CF₃-1H-pyrazol-1-yl 468  27 H H G-1b 4-Me 3-CF₃-1H-pyrazol-1-yl454  28 H H G-1b 6-Me 3-CF₃-1H-pyrazol-1-yl 454  29 H H G-1b 5-Me-6-F3-CF₃-1H-pyrazol-1-yl 473  30 H H G-1b 6-Cl 3-CF₃-1H-pyrazol-1-yl 474 31 Cl H G-1a 2-Cl 4-Br-1H-pyrazol-1-yl 520  32 H H G-1b 6-Br3-CF₃-1H-pyrazol-1-yl 518  33 H H G-1b 6-c-Pr 3-CF₃-1H-pyrazol-1-yl 480 34 F H G-1a 2-Cl 4-Br-1H-pyrazol-1-yl 504  36 H H G-1a 2,6-di-Cl3-CF₃-1H-pyrazol-1-yl 129-132  37 F H G-1a 2-CF₃ 3-CF₃-1H-pyrazol-1-yl114-117  38 H H G-1b 2-Cl 3-CF₃-1H-pyrazol-1-yl 474  39 H H G-1b 6-OCF₃3-CF₃-1H-pyrazol-1-yl 525  40 H H G-1a 2,6-di-Cl 3-Br-1H-pyrazol-1-yl86-89  41 H H G-1b 2-CF₃ 3-CF₃-1H-pyrazol-1-yl 508  42 H CH₃ G-1b 5-CF₃3-CF₃-1H-pyrazol-1-yl 522  43 F H G-3a 5-Cl 3-CF₃-1H-pyrazol-1-yl121-124  44 H CH₃ G-1b 4-OMe 3-CF₃-1H-pyrazol-1-yl 484  45 H CH₃ G-1b6-Me 3-CF₃-1H-pyrazol-1-yl 468  46 F H G-1a 2-Cl 1H-pyrazol-1-yl 424  47F H G-1a 2-Cl 3-Br-1H-pyrazol-1-yl 504  48 H H G-1a 2-Cl 1H-pyrazol-1-yl406  49 H H G-1a 2-Cl 3-Br-1H-pyrazol-1-yl 486  50 H H G-1a 2-Cl1H-1,2,4-triazol-1-yl 407  51 F CH₃ G-1b 4-CF₃ 3-CF₃-1H-pyrazol-1-yl96-99  52 F CH₃ G-1b 6-Me 3-CF₃-1H-pyrazol-1-yl 486  53 F CH₃ G-1b 6-Br3-CF₃-1H-pyrazol-1-yl 552  54 F CH₃ G-1b 5-Cl 3-CF₃-1H-pyrazol-1-yl119-122  55 F CH₃ G-1b 4-OMe 3-CF₃-1H-pyrazol-1-yl 96-99  56 F CH₃ G-1b5-CF₃ 3-CF₃-1H-pyrazol-1-yl 111-115  57 F H G-1b 6-CF₃3-CF₃-1H-pyrazol-1-yl 527  58 F H G-1b 5-CF₃ 3-CF₃-1H-pyrazol-1-yl 527 59 F H G-1b 4-CF₃ 3-CF₃-1H-pyrazol-1-yl 527  60 F H G-1b 5-Cl3-CF₃-1H-pyrazol-1-yl 493  61 F H G-1a 2-OCH₂CN 3-CF₃-1H-pyrazol-1-yl121-124  62 F H G-1a 2-OCH₂C≡CH 3-CF₃-1H-pyrazol-1-yl 96-99  63 H H G-4a3-i-Pr 3-CF₃-1H-pyrazol-1-yl 135-138  64 F H G-1a 2-Cl2H-1,2,3-triazol-2-yl 425  65 F H G-1a 2-Cl 3-CH₃-1H-1,2,4-triazol-1-yl439  66 F H G-1a 2-Cl 1H-1,2,3-triazol-1-yl 425  67 F H G-1a 2-Cl3-CF₃-1H-1,2,4-triazol-1-yl 494  68 F H G-1a 2-F 3-CF₃-1H-pyrazol-1-yl476  69 H H G-1a 2-F 3-CF₃-1H-pyrazol-1-yl 459  70 F H G-1a 2,6-di-F3-CF₃-1H-pyrazol-1-yl 495  71 H H G-1a 2,6-di-F 3-CF₃-1H-pyrazol-1-yl476  72 F CH₃ G-1a 2-Cl 3-CF₃-1H-pyrazol-1-yl 506  73 F CH₃ G-1b 4-Me3-CF₃-1H-pyrazol-1-yl 112-115  74 F CH₃ G-1b 4-Cl 3-CF₃-1H-pyrazol-1-yl506  75 H H G-2a 5-Cl 3-CF₃-1H-pyrazol-1-yl 160-163  76 F H G-4a 3-i-Pr3-CF₃-1H-pyrazol-1-yl 124-127  77 H CH₃ G-1b 2-Cl 3-CF₃-1H-pyrazol-1-yl79-83  78 F CH₃ G-4a 3-Cl 4-Br-1H-pyrazol-1-yl 156-159  79 F CH₃ G-1b2-Cl 3-CF₃-1H-pyrazol-1-yl 506  80 H CH₃ G-1b 6-i-Pre3-CF₃-1H-pyrazol-1-yl 494  81 F H G-4a 3-Me 3-CF₃-1H-pyrazol-1-yl130-133  82 H CH₃ G-1b 6-i-Pr 3-CF₃-1H-pyrazol-1-yl 496  84 F H G-1b6-Me 3-CF₃-1H-pyrazol-1-yl 473  85 F H G-1b 5-Me-6-F3-CF₃-1H-pyrazol-1-yl 491  86 F H G-1b 6-Cl 3-CF₃-1H-pyrazol-1-yl 493 87 F H G-1b 4-Me 3-CF₃-1H-pyrazol-1-yl 473  88 F H G-1b 6-i-Pr3-CF₃-1H-pyrazol-1-yl 499  89 F CH₃ G-4a 3-Cl 3-Br-1H-pyrazol-1-yl 77-81 90 F CH₃ G-4a 3-Cl 3-Ph-1H-pyrazol-1-yl 170-172  91 F H G-4a 3-Br3-CF₃-1H-pyrazol-1-yl 154-158  92 F H G-2a 5-Cl 3-CF₃-1H-pyrazol-1-yl171-174  93 F H G-1a 3-Me 3-CF₃-1H-pyrazol-1-yl 104-107  94 F H G-1a3-OCF₃ 3-CF₃-1H-pyrazol-1-yl 543  95 F H G-1a 3-CF₃3-CF₃-1H-pyrazol-1-yl 526  96 F H G-1a 3-OMe 3-CF₃-1H-pyrazol-1-yl 489 97 F CH₃ G-4a 3-Cl 4-Cl-1H-pyrazol-1-yl 142-145  98 F H G-1a 3-Br3-CF₃-1H-pyrazol-1-yl 536  99 F H G-1a 3-Cl 3-CF₃-1H-pyrazol-1-yl 492100 H H G-2a 3-Cl 3-CF₃-1H-pyrazol-1-yl 474 101 F CH₃ G-4a 3-Cl1H-pyrazol-1-yl 112-116 102 F H G-1a 3-i-Pre 3-CF₃-1H-pyrazol-1-yl 498103 F CH₃ G-4a 3-Cl 3-CF₃-1H-pyrazol-1-yl 170-173 104 F H G-7a H1H-pyrazol-1-yl 107-111 105 F H G-1a 2-Me 3-CF₃-1H-pyrazol-1-yl  97-100106 F H G-1a 2-Br 3-CF₃-1H-pyrazol-1-yl 121-124 107 H H G-1b 6-CF₃3-CF₃-1H-pyrazol-1-yl 509 108 H H G-1b 5-CF₃ 3-CF₃-1H-pyrazol-1-yl 509109 H H G-1b 4-CF₃ 3-CF₃-1H-pyrazol-1-yl 509 110 F H G-4a 3-Br1-CH₃-1H-pyrazol-4-yl 483 111 F H G-1b 6-NO₂ 3-CF₃-1H-pyrazol-1-yl 504112 H H G-1b 5-Cl 3-CF₃-1H-pyrazol-1-yl 475 113 F H G-1b 6-OMe3-CF₃-1H-pyrazol-1-yl 489 114 F H G-4a 3-c-Pr 3-CF₃-1H-pyrazol-1-yl123-126 115 H H G-4a 3-i-Pre 3-CF₃-1H-pyrazol-1-yl 128-131 116 F H G-1a3-i-Pr 3-CF₃-1H-pyrazol-1-yl 500 117 F H G-4a 3-Cl 4-Cl-1H-pyrazol-1-yl300-300 118 F H G-7a H 3-CF₃-1H-pyrazol-1-yl 125-128 119 H CH₃ G-1b 6-Cl3-CF₃-1H-pyrazol-1-yl 87-90 120 H CH₃ G-1b 6-OMe 3-CF₃-1H-pyrazol-1-yl484 121 F H G-1a 2-i-Pr 3-CF₃-1H-pyrazol-1-yl 107-110 122 F H G-4a 3-Cl3-CF₃-1H-pyrazol-1-yl 150-153 123 F CH₃ G-1b 6-i-Pre3-CF₃-1H-pyrazol-1-yl 512 124 H H G-4a 3-CH₃ 3-CF₃-1H-pyrazol-1-yl 456125 F H G-1a 2,6-di-Cl 1H-pyrazol-1-yl 144-148 126 H CH₃ G-1b 4-Cl3-CF₃-1H-pyrazol-1-yl 488 127 F H G-1a 2,6-di-Cl 3-CF₃-1H-pyrazol-1-yl132-135 128 H CH₃ G-1b 6-Br 3-CF₃-1H-pyrazol-1-yl 131-134 129 H CH₃ G-1b6-NO₂ 3-CF₃-1H-pyrazol-1-yl 172-175 130 H CH₃ G-1b 6-OCF₃3-CF₃-1H-pyrazol-1-yl  99-102 131 F H G-4a 3-i-Pre 3-CF₃-1H-pyrazol-1-yl127-130 132 F H G-1a 2,6-di-Cl 3-Br-1H-pyrazol-1-yl 66-69 133 F CH₃ G-1b6-OCF₃ 3-CF₃-1H-pyrazol-1-yl 556 134 F CH₃ G-1b 6-NO₂3-CF₃-1H-pyrazol-1-yl 154-157 135 F CH₃ G-1b 6-Cl 3-CF₃-1H-pyrazol-1-yl117-121 136 F H G-1b 2-Cl 3-CF₃-1H-pyrazol-1-yl 492 137 F H G-1b 2-CF₃3-CF₃-1H-pyrazol-1-yl 526 138 F H G-1b 4-Cl 3-CF₃-1H-pyrazol-1-yl 493139 H H G-1b 4-Cl 3-CF₃-1H-pyrazol-1-yl 475 140 F H G-1b 6-OCF₃3-CF₃-1H-pyrazol-1-yl 543 141 F CH₃ G-1b 6-i-Pr 3-CF₃-1H-pyrazol-1-yl514 142 F CH₃ G-1b 6-OMe 3-CF₃-1H-pyrazol-1-yl 88-92 143 F H G-1a 2-Cl4-Cl-1H-pyrazol-1-yl 458 144 F H G-1a 2-Cl 4-CH₃-1H-pyrazol-1-yl 438 145F H G-1a 2-Cl 1H-1,2,4-triazol-1-yl 425 146 F H G-1a 2-Cl3-Cl-1H-1,2,4-triazol-1-yl 459 147 F H G-1a 2-Cl3-Br-1H-1,2,4-triazol-1-yl 505 * See synthesis example for ¹H NMR data.** See Index Table G for ¹H NMR data.

INDEX TABLE B

Cmpd. m.p. No. R⁵ G (R³)_(n) Q (° C.) M + 1 M − 1  35 H G-1a 2-Cl3-CF₃-1H- 493 pyrazol-1-yl 148 H G-3a 4-Cl 3-CF₃-1H- 200-203pyrazol-1-yl 149 H G-1b H 3-CF₃-1H- 458 pyrazol-1-yl

INDEX TABLE C

Cmpd. m.p. No. R⁷ R⁸ G (R³)_(n) Q (° C.) M + 1 150 CF₃ CH₃ G-1b H3-CF₃-1H-  99-101 pyrazol-1-yl 151 CF₃ CH₃ G-1a 2-Cl 3-CF₃-1H- 510pyrazol-1-yl 158 Br H G-1a 2-Cl 3-CF₃-1H- 129-132 pyrazol-1-yl 159 CH₃ HG-1a 2-Cl 3-CF₃-1H- 106-109 pyrazol-1-yl 160 F H G-1a 2-Cl 3-CF₃-1H-120-124 pyrazol-1-yl

INDEX TABLE D

Cmpd. No. R⁹ R^(2a) G (R³)_(n) Q m.p. (° C.) M + 1 M − 1 152 CH₃ H G-1bH 3-CF₃-1H-pyrazol-1-yl * 406 153 Cl H G-1a 2-Cl 3-CF₃-1H-pyrazol-1-yl124-127 154 I H G-1a 2-Cl 3-CF₃-1H-pyrazol-1-yl 117-119 155 CH₃ CH₃ G-1b6-Me 3-CF₃-1H-pyrazol-1-yl 435 156 I CH₃ G-1b 6-Me 3-CF₃-1H-pyrazol-1-yl547 157 CH₃ H G-1a 2-Cl 3-CF₃-1H-pyrazol-1-yl 89-92

INDEX TABLE E

Cmpd. No. R¹⁰ R^(2a) G (R³)_(n) Q m.p. (° C.) 161 CH₃ H G-1a 2-Cl3-CF₃-1H-pyrazol-1-yl 78-81

INDEX TABLE F

Cmpd. No. R⁵ R⁵¹ G (R³)_(n) Q m.p. (° C.) 162 F CH₂ G-1a 2-Cl3-CF₃-1H-pyrazol-1-yl 134-137 163 H CH₂ G-1a 2-Cl 3-CF₃-1H-pyrazol-1-yl131-134 164 F O G-1a 2-Cl 3-CF₃-1H-pyrazol-1-yl 114-117

INDEX TABLE G Compd. No. ¹H NMR Data (CDCl₃ solution unless indicatedotherwise)^(a) 10 δ 7.91 (s, 1H), 7.75 (d, 1H), 7.67 (m, 2H), 7.49 (dd,1H), 7.38 (d, 1H), 7.07 (t, 1H), 4.83 (s, 2H), 3.97 (s, 3H), 2.74 (t,1H), 0.62-0.82 (m, 4H). ^(a1)H NMR data are in ppm downfield fromtetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet,(t)-triplet, (m)-multiplet, (dd)-doublet of doublets.

Biological Examples of the Invention

General protocol for preparing test suspensions for Tests A-E: the testcompounds were first dissolved in acetone in an amount equal to 3% ofthe final volume and then suspended at the desired concentration (inppm) in acetone and purified water (50/50 mix by volume) containing 250ppm of the surfactant Trem® 014 (polyhydric alcohol esters). Theresulting test suspensions were then used in Tests A-E. Samples wereapplied to plants at either a 10 ppm (**), 40 ppm, 50 ppm (*) or 200 ppm(#) test solution to the point of run-off on the test plants with theequivalent of a rate of 40 g ai/ha, 160 g ai/ha, 200 g ai/ha, or 800 gai/ha, respectively.

Test A

The test suspension was sprayed to the point of run-off on tomatoseedlings. The following day the seedlings were inoculated with a sporesuspension of Botrytis cinerea (the causal agent of gray mold on manycrops) and incubated in a saturated atmosphere at 20° C. for 48 h, andmoved to a growth chamber at 27° C. for 2 days, after which time visualdisease ratings were made.

Test B

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Stagonospora nodorum (also known as Septoria nodorum; thecausal agent of wheat glume blotch) and incubated in a saturatedatmosphere at 20° C. for 48 h, and then moved to a growth chamber at 20°C. for 6 days, after which time visual disease ratings were made.

Test C

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Septoria tritici (the causal agent of wheat leaf blotch)and incubated in a saturated atmosphere at 24° C. for 48 h, and thenmoved to a growth chamber at 20° C. for 21 days, after which time visualdisease ratings were made.

Test D

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporesuspension of Puccinia recondite f. sp. tritici; (the causal agent ofwheat leaf rust) and incubated in a saturated atmosphere at 20° C. for24 h, and then moved to a growth chamber at 20° C. for 6 days, afterwhich time visual disease ratings were made.

Test E

The test suspension was sprayed to the point of run-off on wheatseedlings. The following day the seedlings were inoculated with a sporedust of Erysiphe graminis f. sp. tritici, (the causal agent of wheatpowdery mildew) and incubated in a growth chamber at 20° C. for 7 or 8days, after which time visual disease ratings were made.

Results for Tests A-E are given in Table A. In the Table, a rating of100 indicates 100% disease control and a rating of 0 indicates nodisease control (relative to the controls). A dash (-) indicates no testresults.

TABLE A Cmpd. No Test A Test B Test C Test D Test E  1 0 0 86 0 96  1# 069 93 28 98  2 0 0 43 0 0  2# 0 0 96 0 43  3 0 100 100 99 99  4 0 0 42 00  4# 0 0 46 28 27  5 0 0 17 0 0  5# 0 0 80 28 0  6 0 0 9 0 0  6# 0 9867 28 13  7 0 0 0 0 0  7# 0 0 18 0 0  8 0 0 27 0 0  8# 0 0 88 74 0  9 993 96 9 81  9# 39 99 100 74 96  10 0 99 38 86 0  11 0 89 100 54 43  12 0100 100 99 97  13 0 0 0 32 0  14 0 42 83 32 92  16* — — 100 67 56  17 0100 99 23 92  18 0 100 99 98 98  19 0 99 75 85 64  20 32 99 94 79 40  210 0 — 0 64  22 0 90 — 55 81  23 0 98 — 99 98  24 0 100 — 99 90  25 0 100— 100 98  26 0 99 — 0 81  27 0 92 38 31 21  28 11 99 45 45 59  29 0 9483 68 48  30 0 60 87 31 64  31 0 0 42 98 0  32 0 0 — 0 97  33 0 98 — 6894  34 23 100 94 100 95  35 0 0 89 9 0  36 0 99 — 99 90  37 0 100 — 9799  38 14 0 — 41 69  39 0 0 — 55 72  40 — 99 99 99 89  41 0 0 94 23 40 42 — 0 39 0 0  43 — 0 6 0 0  44 — 78 87 0 0  45 — 100 96 9 90  46 — 10099 94 98  47 — 100 99 98 99  48 — 100 98 0 73  49 — 98 99 9 69  50 — 028 0 0  51 — 100 88 0 84  52 — 100 99 93 99  53 — 100 97 74 96  54* — —96 99 93  55 — 100 97 61 87  56 — 100 97 86 92  57 — — — — —  58 — — — ——  59 — — — — —  60 — — — — —  61 — 0 90 9 21  62 — 99 99 99 94  63 — —— — —  64 — 100 98 100 97  65 — 87 98 0 0  66 — 97 94 28 0  67 — 0 99 00  68 — 100 97 91 99  69 — 60 98 0 69  70 — 100 99 80 97  71 — 92 99 091  72 — 100 100 99 99  73 — — 99 85 90  74 — — 99 27 93  75** — — 24 450  76 — — — — —  77** — — 82 9 64  78** — — 100 94 92  79* — — 99 74 98 80* — — 94 98 73  81** — — 94 98 81  82* — — 88 0 87  84* — 100 98 8994  85* — 100 99 — 95  86* — 100 99 68 95  87* — — 98 80 92  88* — — 9499 98  89** — — 100 99 81  90** — — 99 99 86  91** — — 100 98 73  92** —— — 67 0  93** — — 100 99 69  94** — — 88 73 40  95** — — 87 67 27  96**— — 100 99 73  97** — 100 97 94 94  98** — 64 94 86 84  99** — 59 96 9789 100** — 0 6 0 0 101** — — 96 82 79 102** — — 100 98 13 103** — — 9898 94 104 — — — — — 105 — 100 98 99 98 106 — 100 96 99 97 107 — 0 31 1989 108 — 0 66 0 40 109 — 0 75 0 40 110* — — 90 94 40 111* — — 14 9 0112* — — 94 54 40 113* — — 100 99 97 114** — — 100 100 92 115** — — 2793 40 116** — — — 98 69 117 — — — — — 118 — — — — — 119 — 99 92 93 92120 — 100 92 — 95 121 — 100 95 100 99 122** — — 96 99 87 123* — — 100 9293 124 — 0 94 0 73 125 — 100 99 100 92 126 — 92 92 68 48 127 — 100 99100 98 128 — 100 92 0 93 129 — 0 10 0 0 130 — 93 28 68 72 131* — — 100100 99 132 — 100 99 100 91 133* — 100 92 68 94 134* — 94 43 68 0 135* —100 99 80 95 136* — — 100 99 87 137* — — 94 98 87 138 — — — — — 139 — —— — — 140 — — — — — 141 — — — — — 142* — 100 97 83 98 143 — 100 99 99 99144 — 100 99 97 99 145 — 95 95 0 0 146 — 0 94 0 0 147 — 0 93 0 0 148* 00 9 0 0 149 0 0 43 0 0 150 0 0 48 9 0 151 23 0 87 23 0 152 0 0 0 0 0 153— — — — — 154 — — — — — 155 — — — — — 156 — — — — — 157 — — — — — 158 —— — — — 159 — — — — — 160 — — — — — 161 — — — — — 162** — 0 64 0 0 163 —— — — — 164** — 0 46 0 0

What is claimed is:
 1. A compound selected from Formula 1, N-oxides andsalts thereof,

wherein A is a radical selected from the group consisting of

Z is O or S; R¹ is C₃-C₅ cycloalkyl; or a 4- to 6-membered ringcontaining ring members selected from carbon atoms, 1O atom and 1S atom;R^(2a) and R^(2b) are each independently H, halogen, C₁-C₂ alkyl orC₁-C₂ haloalkyl; or R^(2a) and R^(2b) are taken together as C₂-C₅alkanediyl; G is phenyl, pyridinyl, pyridazinyl or pyrazinyl substitutedwith Q meta or para to the —C(R^(2a))R^(2b)— radical, and optionallysubstituted with up to 3 substituents selected from R³; R³ is halogen,nitro, cyano, C₁-C₅ cyanoalkoxy, C₂-C₅ alkynyloxy, C₂-C₅ alkenyl, C₁-C₅alkyl, C₁-C₅ haloalkyl, C₁-C₅ alkoxy, C₁-C₅ haloalkoxy, C₂-C₅alkoxyalkyl, C₃-C₅ cycloalkyl, C₂-C₅ alkoxycarbonyl or C₃-C₁₂trialkylsilyl; R⁴ is halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl; R⁵ is H,halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl; R⁶ is C₁-C₂ alkyl; R⁷ ishalogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl; R⁸ is H, C₁-C₂ alkyl or C₁-C₂haloalkyl; R⁹ is halogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl; R¹⁰ ishalogen, C₁-C₃ alkyl or C₁-C₃ haloalkyl; R¹¹ is halogen, C₁-C₃ alkyl orC₁-C₃ haloalkyl; m is 0, 1 or 2; Q is a 5-membered unsaturated orpartially unsaturated heterocyclic ring containing ring members selectedfrom carbon atoms and up to 4 heteroatoms independently selected from upto 1O, up to 1S and up to 4 N atoms, wherein up to 2 carbon atom ringmembers are independently selected from C(═O), the ring optionallysubstituted with one substituent on a ring member distal relative to thering member connecting the heteroaromatic ring to the remainder ofFormula 1, said optional substituent selected from R^(12c) on carbonatom ring members and from R^(12n) on nitrogen atom ring members, theheterocyclic ring further optionally substituted with substituentsselected from R^(13c) on carbon atom ring members and R^(13n) onnitrogen atom ring members; each R^(12c) is independently halogen,cyano, C₁-C₃ alkyl, C₁-C₃ haloalkyl, C₁-C₃ alkoxy, C₁-C₃ haloalkoxy orC₂-C₃ alkoxycarbonyl; or a phenyl ring optionally substituted with up to5 substituents independently selected from R¹⁴; or a heteroaromatic ringoptionally substituted with up to 4 substituents independently selectedfrom R^(15c) on carbon atom ring members and from R^(15n) on nitrogenatom ring members; or two R^(12c) bonded to adjacent carbon atoms aretaken together with carbon atom ring members to form a 5- or 6-memberedcarbocyclic or partially aromatic ring; each R^(12n) is independentlyC₁-C₃ alkyl, C₁-C₃ haloalkyl or C₁-C₃ alkoxy; or a phenyl ringoptionally substituted with up to 5 substituents independently selectedfrom R¹⁶; or a heteroaromatic ring optionally substituted with up to 4substituents independently selected from R^(17c) on carbon atom ringmembers and from R^(17n) on nitrogen atom ring members; each R^(13c) isindependently halogen, C₁-C₃ alkyl, C₁-C₃ haloalkyl or C₁-C₃ alkoxy;each R^(13n) is independently C₁-C₃ alkyl, C₁-C₃ haloalkyl or C₁-C₃alkoxy; each R¹⁴, R^(15c), R¹⁶ and R^(17c) is independently halogen,cyano, C₁-C₂ alkyl, C₁-C₂ haloalkyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy;and each R^(15n) and R^(17n) is independently C₁-C₂ alkyl, C₁-C₂haloalkyl or C₁-C₂ alkoxy.
 2. A compound of claim 1 wherein: Z is O; R¹is C₃-C₄ cycloalkyl; or a 4- to 5-membered ring containing ring membersselected from carbon atoms, 1O atom and 1S atom; R^(2a) is H, CH₃, CF₃or CHF₂; R^(2b) is H or CH₃; or R^(2a) and R^(2b) are taken together asC₂ or C₃ alkanediyl; G is phenyl or pyridinyl substituted with Q meta orpara to the —C(R^(2a))R^(2b)— radical, and optionally substituted withup to 2 substituents selected from R³; R³ halogen, cyano, C₁-C₅ alkyl,C₁-C₅ haloalkyl, C₁-C₅ alkoxy, C₁-C₅ haloalkoxy, C₂-C₅ alkoxyalkyl,C₃-C₅ cycloalkyl; R⁴ is halogen, C₁-C₂ alkyl or C₁-C₂ haloalkyl; R⁵ isH, halogen, C₁-C₂ alkyl or C₁-C₂ haloalkyl; R⁶ is CH₃; R⁷ is halogen,C₁-C₂ alkyl or C₁-C₂ haloalkyl; R⁸ is H or CH₃; R⁹ is halogen, C₁-C₂alkyl or C₁-C₂ haloalkyl; R¹⁰ is F, Cl, Br, CH₃, CHF₂ or CF₃; R¹¹ is F,Cl, Br, CH₃, CHF₂ or CF₃; Q is selected from;

each R^(12c) is independently halogen, cyano, C₁-C₂ alkyl, C₁-C₂haloalkyl, C₁-C₂ alkoxy or C₁-C₂ haloalkoxy; each R^(12n) isindependently C₁-C₂ alkyl or C₁-C₂ haloalkyl; each R^(13c) isindependently halogen, C₁-C₂ alkyl, C₁-C₂ haloalkyl or C₁-C₂ alkoxy;each R^(13n) is independently C₁-C₂ alkyl or C₁-C₂ haloalkyl; each R¹⁴,R^(15c), R¹⁶ and R^(17c) is independently halogen, CH₃ or C₁ haloalkyl;and R^(15n) and R^(17n) is independently C₁-C₂ alkyl or C₁-C₂ haloalkyl.3. A compound of claim 2 wherein: A is selected from the groupconsisting of A-1, A-2, A-3 and A-4; R¹ is cyclopropyl; or a 4-memberedring containing ring members selected from carbon atoms, 1O atom and 1Satom; R^(2a) is H, F or CH₃; R^(2b) is H; or R^(2a) and R^(2b) are takentogether as C₂ alkanediyl; G is phenyl or pyridinyl substituted with Qmeta or para to the —C(R^(2a))R^(2b)— radical, and optionallysubstituted with 1 substituent selected from R³; R³ is halogen, CH₃,CF₃, CHF₂, OCH₃, OCF₃, CH₂CH₂OCH₃ or cyclopropyl; R⁴ is halogen, CH₃ orC₁ haloalkyl; R⁵ is H, F, Cl, Br, CH₃, CHF₂ or CF₃; R⁷ is halogen, CH₃or C₁ haloalkyl; R⁹ is F, Cl, Br, CHF₂ or CF₃; Q is selected from Q-1through Q-19; R^(12c) is independently halogen, CH₃ or C₁ haloalkyl;R^(12n) is C₁-C₂ alkyl; each R^(13c) is independently halogen, CH₃ or C₁haloalkyl; each R^(13n) is C₁-C₂ alkyl; each R¹⁴, R^(15c), R¹⁶ andR^(17c) is independently F, Cl, Br, CH₃, CHF₂ or CF₃; and each R^(15n)and R^(17n) is independently C₁-C₂ alkyl.
 4. A compound of claim 3wherein: A is selected from the group consisting of A-1, A-2 and A-3; R¹is cyclopropyl, 3-oxetanyl or 3-thietanyl; G is phenyl substituted withQ meta or para to the —C(R^(2a))R^(2b)— radical, and optionallysubstituted with 1 substituent selected from R³; R³ is Cl, Br, CH₃, CF₃,CHF₂, OCH₃ or cyclopropyl; R⁴ is F, Cl, Br, CH₃, CHF₂ or CF₃; R⁵ is F orCl; R⁷ is F, Cl, Br, CH₃, CHF₂ or CF₃; R⁹ is F, Cl, Br, CHF₂ or CF₃; Qis selected from

each R^(12c) is independently F, Cl, Br, CH₃, CHF₂ or CF₃; each R^(12n)is CH₃; each R^(13c) is independently F, Cl, Br, CH₃, CHF₂ or CF₃; eachR^(13n) is CH₃; and each R^(15n) and R^(17n) is CH₃.
 5. A compound ofclaim 2 wherein: A is selected from the group consisting of A-1 and A-2;R¹ is cyclopropyl; G is phenyl substituted with Q para to the—C(R^(2a))R^(2b)— radical, and unsubstituted with R³; R⁴ is CHF₂; Q isselected from Q-9A and Q-9B; and R^(12c) is CF₃.
 6. A compound of claim3 wherein: A is A-1; R¹ is cyclopropyl; G is pyridinyl substituted withQ meta or para to the —C(R^(2a))R^(2b)— radical, and optionallysubstituted with 1 substituent selected from R³; R³ is Cl; R⁴ is CHF₂; Qis Q-9A; and R^(12c) is CF₃.
 7. A compound of claim 1 which is selectedfrom the group consisting of:N-[[2-chloro-4-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl]methyl]-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1H-pyrazole-4-carboxamide;andN-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[[3-[3-(trifluoromethyl)-1H-pyrazol-1-yl]phenyl]methyl]-1H-pyrazole-4-carboxamide.8. A fungicidal composition comprising (a) a compound of claim 1; and(b) at least one other fungicide.
 9. A fungicidal composition comprising(a) a compound of claim 1; and (b) at least one additional componentselected from the group consisting of surfactants, solid diluents andliquid diluents.
 10. A method for controlling plant diseases caused byfungal plant pathogens comprising applying to the plant or portionthereof, or to the plant seed, a fungicidally effective amount of acompound of claim 1.